Biobased rubber modifiers for polymer blends

ABSTRACT

Compositions of polymer blends of polyvinylchloride (PVC) or polymethylmethacrylate (PMMA) or polyoxymethylene (POM) and polyhydroxyalkanoate (PHA) are described. In certain embodiments, the PHA is a poly-3-hydroxybutyrate-co-4-hydroxybutyrate copolymer having a weight percent 4-hydroxybutyrate of 30-45%. In other embodiments the PHA is a multiphase P3HB-4HB copolymer blend having one phase fully amorphous. The PHA is mixed with the PVC or PMMA or POM to optimize its optical, thermal and mechanical properties. In certain embodiments, the polymer is branched with optionally additives that improve properties. Methods of making the compositions of the invention are also described. The invention also includes articles, films and laminates comprising the compositions.

RELATED APPLICATIONS

This application is the U.S. National Stage of International ApplicationNo. PCT/US2013/055624, filed Aug. 19, 2013, which designates the U.S.,published in English, and claims the benefit of U.S. ProvisionalApplication No. 61/684,583 filed on Aug. 17, 2012; 61/716,858 filed onOct. 22, 2012; 61/726,873 filed on Nov. 15, 2012; 61/754,467 filed onJan. 18, 2013; 61/764,180 filed on Feb. 13, 2013 and 61/812,944 filed onApr. 17, 2013. The entire teachings of the above applications areincorporated herein by reference.

BACKGROUND OF THE INVENTION

Production of polymers that are derived from renewable resources isexpected to grow to 3.45 million tons by the year 2020 which representsa current annual growth rate of approximately 37% (Plastics Engineering,February 2010, p 16-19). The drivers for growth of biobased plasticsinclude the contribution to global warming from production ofpetroleum-based plastics, the need to reduce our dependence on limitedsupplies of petroleum oil, the fluctuating petroleum oil prices as wellas environmental disposal problems of common petroleum-based plastics.While the objective for the manufacture of biobased plastics is tomaximize the total “renewable” carbon content of polymer products asmuch as possible, some existing large volume biobased plastics haveunique material properties which can be utilized as value-addedmodifiers for existing petroleum-based plastics and composites.

Examples of biobased polymers include polyethylene (PE) produced fromsugarcane ethanol (Braskem's Green Polyethylene), polylactic acid (PLA)made from corn sugar (Nature Works Ingeo™ PLA) and polyhydroxyalkanoates(PHA's) produced by the fermentation of glucose (U.S. Pat. Nos.6,593,116 and 6,913,911, US Patent Pub. No. 2010/0168481). Reportedly,the most commercially important bioplastics by the year 2020 willinclude starch-based polymers, PLA, polyethylene, polyethyleneterephthalate (PET), PHA and epoxy resins (Shen et al., (2010),Biofuels, Bioproducts and Biorefining, vol. 4, Iss. 1, p 25-49).

Polyhydroxyalkanoates (PHAs) are perhaps uniquely positioned to be valueadded modifiers for plastics as they can be produced with a range ofmaterial properties from hard and brittle to soft and flexible. PHAs arenaturally produced by numerous microorganisms in diverse environments.Through genetic-modification of these microbes, hundreds of differenttypes of biobased PHA homopolymer and copolymer materials have beendeveloped (Lee (1996), Biotechnology & Bioengineering 49:1-14; Braunegget al. (1998), J. Biotechnology 65:127-161; Madison, L. L. and Huisman,G. W. (1999), Metabolic Engineering of Poly-3-Hydroxyalkanoates; FromDNA to Plastic, in: Microbiol. Mol. Biol. Rev. 63:21-53). However basedon these unique properties and the demonstration of their performancebenefits, it is also possible to chemically synthesize other PHApolymers from renewable or petroleum resources to achieve similarperformance advantages.

SUMMARY OF THE INVENTION

Described herein are polymer blend compositions of polyvinyl chloride(PVC) or polymethylmethacrylate (PMMA) or polyoxymethylene (POM) withpolyhydroxyalkanoates (PHAs) that have improved properties including butnot limited to improved processability, impact strength, tearresistance, and toughness.

In a first aspect of the invention, the composition is a polymer blendof a polyvinyl chloride (PVC) polymer and a biobased non-extractable,non-volatile plasticizing polyhydroxyalkanoate copolymer or blendthereof (PHA), wherein the PHA comprises a copolymer of3-polyhydroxybutytrate and one more monomers selected from lactic acid,3-hydroxypropionic acid (3HP), 4-hydroxybutyrate (4HB),5-hydroxyvalerate (5HV), 3-hydroxyhexanoate (3HH), 6-hydroxyhexanoate(6HH) and 3-hydroxyoctanoate (3HO), wherein the monomer content is about25-90% of the weight of the PHA (for example about 30% to about 75%, orabout 25% to about 40%) and wherein the PHA unexpectedly improves thematerial performance of the PVC polymer blend. As described herein, itwas found that for improving properties of soft (flexible) PVC products,including films and the like, the addition of PHA having a low glasstransition temperature (Tg) component and a relatively low percentcrystallinity (<40%) is required (for example, about 26-45%, about30-40% or about 28-38%). For modification of rigid PVC, it was useful toadd PHA's with a low Tg as the major component but having a percentcrystallinity even lower (<10%, for example about 0.5 to 5 percent,about 1 to 8%, about 2-5% about 3%, about 4%, about 5%, about 6%, about7%, about 8%, about 9%). The most desirable aspects of the PHA'ssuitable for practicing the invention are their combination of materialproperties, in particular glass transition temperature, percentcrystallinity and degree of miscibility with polymer resins such as PVC,PMMA or POM. In general, PHA copolymers with low glass transitiontemperatures have a low degree of crystallinity and are mostly amorphousmaterial having properties very similar to a rubber-type polymer butadditionally have some level of miscibility with the polymer resin ofinterest. PHA's having partial or complete miscibility with PVC or otherresins are advantageous. It is noted that highly crystalline PHA's suchas the homopolymer poly-3-hydroxybutyrate (P3HB) or copolymers ofpoly-3-hydroxybutyrate-co-3-hydroxyvalerate by themselves do not possessthe necessary properties but when combined with the compositions of theinvention in a “PHA” blend then the “PHA” blend is used as the modifier.Other key aspects of the invention include the selection of stabilizerpackages chosen such that they do not reduce the benefits of the PHAmodifier by thermally degrading the PHA during melt processing of theblend. Additionally in certain embodiments of the any of the aspects ofthe invention described herein, the PHA copolymer has a percentcrystallinity of the PHA is about 0.2 to 1% as measured by DSC. Inanother embodiment of any of the aspects described herein the thesolubility parameter of the monomer of the copolymer is about 17 toabout 21 (δ_(total) (J/cm³)^(1/2)).

In a second aspect, the PHA of the composition is a PHA copolymer of3-polyhydroxybutytrate and one more monomers selected from the groupcomprising lactic acid, 3-hydroxypropionic acid (3HP), 4-hydroxybutyrate(4HB), 5-hydroxyvalerate (5HV), 3-hydroxyhexanoate (3HH),6-hydroxyhexanoate (6HH) and 3-hydroxyoctanoate (3HO) or blend thereof.In an embodiment of the first aspect, the copolymers compriseP3HB-co-4HB, P3HB-co-5HV and P3HB-co-6HH with a comonomer percent from25-90% by weight. Poly-3-hydroxybutyrate-co-3-hydroxyvalerate is notpart of the invention because it forms a very highly crystalline PHA(isodimorphic structure) material which is not suitable for theapplications described herein.

In a third aspect, the PHA copolymer is a multiphase copolymer blend ofPHA, having an amorphous (flexible) rubber phase with a T_(g) betweenabout −15° C. and about −45° C. and is between about 2 weight % to about45 weight % of the total PHA in the composition. Preferably the rubberphase is 5-30% by weight of the PHA copolymer blend. In a fourth aspect,the multiphase copolymer blend of PHA comprises at least two phases. Ina fifth aspect, the multiphase copolymer blend includes a PHA copolymeras described above and a poly-3-hyroxybutyrate homopolymer. In a sixthaspect, the PHA is a two phase PHA copolymer with greater than 11% 4HBcomonomer content of the total PHA polymer. In a seventh aspect, the PHAcomprises an amorphous rubber phase having 3-hydroxybutyrate (3HB) and4-hydroxybutyrate (4HB) comonomer segments with a weight % 4HB of about25% to about 90% of the PHA composition. In an eighth aspect, the PHAcomprises an amorphous rubber phase having 3-hydroxybutyrate (3HB) and4-hydroxybutyrate (4HB) with a weight % 4HB of about 25% to about 55% inthe PHA composition. In a ninth aspect the PHA comprises an amorphousrubber phase having 3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB)with a weight % 4HB of about 25% to about 35% in the PHA composition. Ina tenth aspect, the PHA comprises an amorphous rubber phase having nomelting point. In an eleventh aspect, the PHA is selected from a blendof 18-22% P3HB and 77-83% P3HB-4HB copolymer with 8-14% 4HB by weight; ablend of 34-38% P3HB, a blend of 22-26% P3HB-4HB copolymer with 8-14%4HB by weight and 38-42% P3HB-4HB copolymer with 25-33% 4HB by weight; ablend of 10-15% P3HB, 46-50% P3HB-4HB copolymer with 8-14% 4HB by weightand 38-42% P3HB-4HB copolymer with 25-33% 4HB by weight or TianjinSOGREEN® (PHA) with 30% 4HB content. In a twelfth aspect, the PHApolymer is included in a PHA masterbatch comprising a PHA crosslinkedwith a peroxide and a co-agent blended with anacrylonitrile-styrene-acrylate terpolymer or chlorinated polyethylene.

In a first embodiment of any one or more of the first to twelfthaspects, the PHA has an average molecular weight range of about 50,000to about 2.5 million g/mole. In a second embodiment of any one or moreof the first to twelfth aspects and further including the firstembodiment, the PVC has a K-value of between 57 and 70. In a thirdembodiment of any one or more of the first to twelfth aspects, orfurther including the first or second embodiment, the amount of PHA inthe polymer composition (PHA plus PVC, PMMA or POM plus any otherpolymer present) is about 1% to about 50% by weight of the totalcomposition. In a fourth embodiment of any one or more of the first totwelfth aspects, or further including the first, second and or thirdembodiment, the amount of PHA in the polymer composition is about 3% toabout 40% by weight of the total composition or the amount of PHA in thepolymer composition is about 20% to about 30% by weight of the totalcomposition.

In a fifth embodiment of any one or more of the first to twelfthaspects, or further including the first, second, third and/or fourthembodiment, the composition further includes a branching agent and aco-agent. Branching agents are highly reactive molecules which form freeradicals. When blended with polymers, the free radicals formed by thebranching agents then react with the polymer chain to form a polymerfree radical which is then able to chemically link itself to anotherpolymer chain thereby forming a branch or crosslink. These are agentsare selected from any suitable initiator known in the art, such asperoxides, azo-derivatives (e.g., azo-nitriles), peresters, andperoxycarbonates. Branching agents are added to the polymers at 0.05%,0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 1.0%, 1.2%, 1.5%, 1.7%or 2% by weight of the PHA polymer. In a preferred embodiment, thebranching agent is reactively extruded with the PHA prior to blendingthe PHA with a rigid PVC polymer. As shown in the examples, the branchedPHA improves the impact resistance of the rigid PVC without diminishingother physical properties of the PHA/PVC blend such as flexural modulus,tensile strength and toughness. In a further embodiment, co-agents orcrosslinking agents are optionally added during reactive extrusion ofthe branching agent with the PHA to enhance the branching effect.Co-agents for reacting with the PHA polymer include, for example,diallyl phthalate, pentaerythritol tetraacrylate, trimethylolpropanetriacrylate, pentaerythritol triacrylate, dipentaerythritolpentaacrylate, diethylene glycol dimethacrylate, bis(2-methacryloxyethyl)phosphate, or combinations thereof, anepoxy-functional styrene-acrylic polymer, an epoxy-functional acryliccopolymer, an epoxy-functional polyolefin copolymer, an oligomercomprising a glycidyl group with an epoxy functional side chain, anepoxy-functional poly(ethylene-glycidyl methacrylate-co-methacrylate),or combinations thereof. The co-agent can be premixed with a nonreactiveplasticizer then added to the PH.

In a sixth embodiment of any one or more of the first to twelfthaspects, or further including the first, second, third, fourth and/orfifth embodiment, the composition further includes one or more additives(e.g., plasticizers, clarifiers, nucleating agents, thermal or oxidativestabilizers, inorganic fillers, anti-slip agents, compatibilizers,blocking agents or a combination thereof). Addition of inert inorganicfillers such as calcium carbonate or silica to the PHA copolymer'shaving high comonomer content (>25% by weight), help reduce thetackiness of the PHA “rubber” and make it easier to handle and processwith the PVC. In certain compositions of the invention (including theaspects and embodiments above, the additives are biobased (e.g., thebiobased content is between 5% and 100%). In a sixth embodiment of anyone or more of the first to the twelfth aspects of the invention andoptionally including one or more of the embodiments described, the PHAis added between 5 and 50 parts per hundred (phr) polyvinyl chloride. Ina seventh embodiment of one or more of the first to twelfth aspects andoptionally further including one or more of the embodiments described,the composition is optically transparent. In an eighth embodiment of oneor more of the first to twelfth aspects and optionally including one ormore of the embodiments described, the PVC polymer and PHA polymer aremiscible. In a ninth embodiment of one or more of the first to twelfthaspects and optionally including one or more of the embodimentsdescribed, the composition is a flexible or rigid PVC and PHAcomposition. In a tenth embodiment of one or more of the first totwelfth aspects and optionally including one or more of the embodimentsdescribed, the biobased PHA is between about 40% and about 100% biobasedcontent. In an eleventh embodiment of any of the compositions or methodsdescribed, the composition has a biobased content of 5-100% (e.g.,5%-20%, 10%-30%, 15%-40%, 20-50%, 25-60%, 30-70%, 40-100%, 40-70%,40-80%, greater than 80% to about 100%, 90%, 91%, 92%, 93%, 94%, 95%,96%, 97%, 98%, 99%, 99.5% or 100%).

In a seventh embodiment of any one or more of the one to twelfthaspects, the PHA copolymer or blend is thermolyzed.

A method of preparing a polyvinyl chloride (PVC)/polyhydroxyalkanoate(PHA) polymer blend composition, comprising melt blending thecomposition of the invention as described above using a single or twinscrew extruder, two-roll mill, Banbury mixer or the like thereby forminga polymer composition of PVC and PHA are also described. The PHA can bebranched or crosslinked using reactive extrusion prior to blending withthe PVC. The compositions of any of the aspects or embodiments of theinvention can be produced as a PHA impact modifier masterbatch, a film,an article (e.g., an article that is used in medical treatments), sheetor multilayer laminate. In certain applications, the article has greatertensile elongation with greater tensile toughness than a correspondingpolymer article consisting only of PVC polymer with no PHA added.

In a seventh embodiment of any of the first to twelfth aspects orincluding any one or more of the embodiments described above, thecompositions further comprise an impact modifies, e.g., a modifierproduced by graft polymerization of acrylates or methacrylates withbutadiene rubber and styrene (acrylate-butadiene-styrene (ABS) andmethacrylate-butadiene-styrene (MBS),

In certain embodiments of the invention, the PHA copolymer is furtherblended with another biobased PHA for use in the compositions. These PHApolymer, copolymer and blends comprise the following polymers alone orin combination: poly(3-hydroxybutyrate) homopolymer, apoly(3-hydroxybutyrate-co-4-hydroxybutyrate), apoly(3-hydroxybutyrate-co-3-hydroxyvalerate), apoly(3-hydroxybutyrate-co-5-hydroxyvalerate), or apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with the proviso that thePHA composition is not 100% poly(3-hydroxybutyrate) homopolymer or 100%poly(3-hydroxybutyrate-co-3-hydroxyvalerate) as these polymers have ahigh degree of crystallinity and are not suitable for practicing thisinvention; a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15%4-hydroxybutyrate content, apoly(3-hydroxybutyrate-co-5-hydroxyvalerate) with 5% to 15%5-hydroxyvalerate content, or apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15%3-hydroxyhexanoate content; a) a poly(3-hydroxybutyrate) homopolymerblended with b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate); a) apoly(3-hydroxybutyrate) homopolymer blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate); a) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyvalerate)); a) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanote, or a) apoly(3-hydroxybutyrate-co-3-hydroxyvalerate),) blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate); a) apoly(3-hydroxybutyrate) homopolymer blended with b) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 5% to 15%4-hydroxybutyrate content; a) a poly(3-hydroxybutyrate) homopolymerblended with b) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5%to 22% 3-hydroxyvalerate content; a) a poly(3-hydroxybutyrate)homopolymer blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 3% to 15%3-hydroxyhexanoate content; a) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 5% to 15%4-hydroxybutyrate content blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5% to 22%3-hydroxyvalerate content; a) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15%4-hydroxybutyrate content blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 3% to 15%3-hydroxyhexanoate content or a) apoly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5% to 22%3-hydroxyvalerate content blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 3% to 15%3-hydroxyhexanoate content, a) a poly(3-hydroxybutyrate) homopolymerblended with b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and theweight of polymer a) can be 5% to 95% of the combined weight of polymera) and polymer b); a) a poly(3-hydroxybutyrate) homopolymer blended withb) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and the weight ofpolymer a) can be 5% to 95% of the combined weight of polymer a) andpolymer b); a) a poly(3-hydroxybutyrate) homopolymer blended to with b)a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and the weight ofpolymer a) can be 5% to 95% of the combined weight of polymer a) andpolymer b); a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) blendedwith b) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and the weight ofpolymer a) can be 5% to 95% of the combined weight of polymer a) andpolymer b); a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) blendedwith b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and the weightof polymer a) can be 5% to 95% of the combined weight of polymer a) andpolymer b); or a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) blendedwith b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and the weightof polymer a) can be 5% to 95% of the combined weight of polymer a) andpolymer b) or the weight of polymer a) is 20% to 60% of the combinedweight of polymer a) and polymer b) and the weight of polymer b) or 40%to 80% of the combined weight of polymer a) and polymer b).

In other embodiments, the biobased PHA comprises a)poly(3-hydroxybutyrate) homopolymer blended with b) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50%4-hydroxybutyrate content; a) a poly(3-hydroxybutyrate) homopolymerblended with b) a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a20% to 50% 5-hydroxyvalerate content; a) a poly(3-hydroxybutyrate)homopolymer blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50%3-hydroxyhexanoate content; a)poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 5% to 15%4-hydroxybutyrate content blended with b) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50%4-hydroxybutyrate content; a)poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 5% to 15%4-hydroxybutyrate content blended with b) apoly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50%5-hydroxyvalerate content; a) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15%4-hydroxybutyrate content blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50%3-hydroxyhexanoate content; a) apoly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5% to 22%3-hydroxyvalerate content blended with b)poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50%4-hydroxybutyrate content; a) apoly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5% to 22%3-hydroxyvalerate content blended with b) apoly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50%5-hydroxyvalerate content; a) apoly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5% to 22%3-hydroxyvalerate content blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50%3-hydroxyhexanoate content; a) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 3% to 15%3-hydroxyhexanoate content blended with b) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50%4-hydroxybutyrate content; a) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 3% to 15%3-hydroxyhexanoate content blended with b) apoly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50%5-hydroxyvalerate; or a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)with a 3% to 15% 3-hydroxyhexanoate content blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50%3-hydroxyhexanoate content; a) a poly(3-hydroxybutyrate) homopolymerblended with b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a20-50% 4-hydroxybutyrate content and the weight of polymer a) can be 5%to 95% of the combined weight of polymer a) and polymer b); a) apoly(3-hydroxybutyrate) homopolymer blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 20% to 50%5-hydroxyvalerate content and the weight of polymer a) can be 5% to 95%of the combined weight of polymer a) and polymer b); a) apoly(3-hydroxybutyrate) homopolymer blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50%3-hydroxyhexanoate content and the weight of polymer a) can be 5% to 95%of the combined weight of polymer a) and polymer b); a) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 5% to 15%4-hydroxybutyrate content blended with b)poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50%4-hydroxybutyrate content and the weight of polymer a) is 5% to 95% ofthe combined weight of polymer a) and polymer b); a) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 5% to 15%4-hydroxybutyrate content blended with b)poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50%5-hydroxyvalerate and the weight of polymer a) can be 5% to 95% of thecombined weight of polymer a) and polymer b); a) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 5% to 15%4-hydroxybutyrate content blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50%3-hydroxyhexanoate content and the weight of polymer a) is 5% to 95% ofthe combined weight of polymer a) and polymer b); a) apoly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5% to 22%3-hydroxyvalerate content blended with b)poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50%4-hydroxybutyrate content and the weight of polymer a) is 5% to 95% ofthe combined weight of polymer a) and polymer b); a) apoly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5% to 22%3-hydroxyvalerate content blended with b) apoly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50%5-hydroxyvalerate and the weight of polymer a) can be 5% to 95% of thecombined weight of polymer a) and polymer b); a) apoly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5% to 22%3-hydroxyvalerate content blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50%3-hydroxyhexanoate content and the weight of polymer a) can be 5% to 95%of the combined weight of polymer a) and polymer b); a) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 3% to 15%3-hydroxyhexanoate content blended with b) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50%4-hydroxybutyrate content and the weight of polymer a) can be 5% to 95%of the combined weight of polymer a) and polymer b); a) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 3% to 15%3-hydroxyhexanoate content blended with b) apoly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50%5-hydroxyvalerate and the weight of polymer a) can be 5% to 95% of thecombined weight of polymer a) and polymer b); or a) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 3% to 15%3-hydroxyhexanoate content blended with b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50%3-hydroxyhexanoate content and the weight of polymer a) can be 5% to 95%of the combined weight of polymer a) and polymer b), wherein thecomposition comprises 20% to 60% of the combined weight of polymer a)and polymer b) and the weight of polymer b can be 40% to 80% of thecombined weight of polymer a) and polymer b).

In other embodiments, polymer a) and polymer b) of the PHA compositionare further blended with polymer c) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20% to 50%4-hydroxybutyrate content, c) apoly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50%5-hydroxyvalerate content or with c) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 5% to 50%3-hydroxyhexanoate content.

In the embodiments of the invention, the PHA for use in the compositionsdoes not include 100% PLA, 100% P3HB orpoly-3-hydroxybutyrate-co-3-polyhydroxyvalerate (isodimorphic).

The composition of any of the embodiments or aspects described herein,further comprising at least one thermal stabilizer, co-stabilizer,plasticizer or antioxidant.

In any of the embodiments or aspects above, the composition comprises apolymer blend of a polyvinyl chloride (PVC) polymer and a biobasednon-extractable nonvolatile plasticizing polyhydroxyalkanoate copolymeror blend thereof (PHA), wherein the PHA includes a3-polyhydroxybutytrate-co-4-polyhydroxybutyrate copolymer and improvesperformance of the PVC polymer blend. The copolymer is a multiphasecopolymer blend of PHA, having an amorphous rubber phase with a T_(g)between about −15° C. and about −45° C. and is between about 5 weight %to about 45 weight % of the total PHA in the composition having leasttwo phases, for example, the multiphase copolymer blend includes apoly-3-hydroxybutytrate-co-4-polyhydroxybutyrate copolymer and apoly-3-hyroxybutyrate homopolymer and optionally contains 11% 4HBcontent of the total PHA and optionally branched or crosslinked,branched by a peroxide and a co-agent additionally the PHA/PVC blendincludes a plasticizer, a barium/zinc stabilizer and an epoxidzedsoybean oil and in some embodiments, the plasticizer is diisononyladipate.

In a further aspect of the invention, the composition includes a polymerblend of a polyvinyl chloride (PVC) polymer and a biobasednon-extractable nonvolatile plasticizing polyhydroxyalkanoate polymer,copolymer or blend thereof (PHA), wherein copolymer is a multiphasecopolymer blend of PHA, having an amorphous rubber phase with a T_(g)between about −15° C. and about −45° C. and is between about 5 weight %to about 45 weight % of the total PHA in the composition having apoly-3-hydroxybutytrate-co-4-polyhydroxybutyrate copolymer having 11%4HB content and a poly-3-hyroxybutyrate homopolymer branched orcrosslinked, branched by a peroxide and a co-agent, diisononyl adipate,a barium/zinc stabilizer and an epoxidzed soybean oil.

In a further aspect of the invention, the composition includes a polymerblend of a polymethylmethacrylate (PMMA) polymer or polyoxymethylene(POM) polymer and a biobased non-extractable nonvolatile plasticizingpolyhydroxyalkanoate copolymer or blend thereof (PHA), wherein the PHAimproves performance of the PMMA or POM polymer blend, wherein the PHAimproves performance of the PVC polymer blend, wherein the PHA comprisesa copolymer of 3-polyhydroxybutytrate and one more monomers selectedfrom lactic acid, 3-hydroxypropionic acid (3HP), 4-hydroxybutyrate(4HB), 5-hydroxyvalerate (5HV), 3-hydroxyhexanoate (3HH),6-hydroxyhexanoate (6HH) and 3-hydroxyoctanoate (3HO), wherein themonomer content is about 25-90% of the weight of the PHA. In certainembodiments, the PHA copolymer has an amorphous rubber phase with aT_(g) between about −15° C. and about −45° C. and is between about 5weight % to about 45 weight % of the total PHA in the composition. Inother embodiments, the copolymer of blend is apoly-3-hydroxybutytrate-co-4-polyhydroxybutyrate copolymer having 11%4HB content and a poly-3-hyroxybutyrate homopolymer branched orcrosslinked, branched by a peroxide and a co-agent, diisononyl adipate,a barium/zinc stabilizer and an epoxidized soybean oil.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing will be apparent from the following more particulardescription of example embodiments of the invention, as illustrated inthe accompanying drawings in which like reference characters refer tothe same parts throughout the different views. The drawings are notnecessarily to scale, emphasis instead being placed upon illustratingembodiments of the present invention.

The foregoing will be apparent from the following more particulardescription of example embodiments of the invention, as illustrated inthe accompanying drawings in which like reference characters refer tothe same parts throughout the different views. The drawings are notnecessarily to scale, emphasis instead being placed upon illustratingembodiments of the present invention.

FIG. 1 is a plot showing melt viscosity vs. shear rate plot @160° C. forPVC with 18 phr DIDP plasticizer (control sample 21—crosses); PVC with10 phr KANE ACE™ B22 impact modifier and 18 phr DIDP (sample18—diamonds); PVC with 28 phr PHA E no DIDP (sample 20—circles).

FIG. 2 is a plot showing melt strength vs. shear rate plot @160° C. forPVC with 18 phr DIDP plasticizer (control sample 20—squares); PVC with10 phr KANE™ ACE B22 impact modifier and 18 phr DIDP (sample18—circles); PVC with 28 phr PHA E no DIDP (sample 21—plus).

FIG. 3 is a TGA curve of % eight loss versus temperature for a PVC+18phr DIDP sample. Also shown is the derivative of this curve with thetemperature at maximum rate loss shown at the peaks of the curve.

FIG. 4 is an overlay plot of the TGA curves and their derivatives forPVC+18 phr DIDP (dashed line), PVC+10 phr PHA E+ 18 phr DIDP (solidline) and PVC+ 28 phr PHA E (dash-dot curve).

FIG. 5 is a plot showing melt strength versus frequency for flexible PVC(diamonds), flexible PVC/KANE ACE™ PA-20 acrylic polymer @5 phr(squares), flexible PVC/PHA C @5 phr (triangles) and flexible PVC/PHA C@10 phr (crosses).

FIG. 6 Plot showing the tensile toughness of PMMA (PLEXIGLAS™ 8N) vs.weight % PHA in blends of PMMA with PHA C (diamonds) or PHA G (squares).

FIG. 7 Plot of melt viscosity vs. shear rate for PMMA (PLEXIGLAS™ 8N)and PMMA (PLEXIGLAS™ 8N) with 10% PHA G by weight at 160° C. Plot showsthat addition of PHA G has no effect on the thermal stability of PMMA.

FIG. 8 Plot of POM Notched Izod impact strength vs. weight % PHA forblends of POM (KEPITAL™ F20-03(diamonds) and F30-03 (squares)) with PHAC. Also included for comparison is the impact strength for KEPITAL TE-21(star) which contains 5% by weight TPU as an impact modifier.

DETAILED DESCRIPTION OF THE INVENTION

A description of example embodiments of the invention follows.

Polymer blend compositions of polyvinyl chloride (PVC) andpolyhydroxyalkanoates (PHAs) having improved mechanical, thermal andoptical properties including improved processability are described. Inone aspect of the invention, the composition is a polymer blend of apolyvinyl chloride (PVC) polymer and a biobased non-extractablenon-volatile plasticizing polyhydroxyalkanoate polymer, copolymer orblend thereof (PHA). The PHA improves the mechanical performance andproperties of rigid to flexible PVC such as: plasticization, impactstrength, tear strength, UV stability, optical clarity and meltstability and in some circumstances improves the application ranges forPVC materials. For example, the PHA component improves impact properties(e.g., strength, durability, breakability), the PHA is a non-extractiblenon-volatile plasticizing PHA (e.g., the PHA imparts more efficientplasticization than the traditional plasticizers, and it's not volatileso there is no leaching or reduction of the plasticizing effect.Further, the PHA imparts an expanded process window (e.g., in somecircumstances from miscibility and crystallinity properties of the PHA).

Surprisingly, it was found that the PHA compositions when added to thePVC provide low temperature flexibility even at high molecular weightsand allows the compositions to have a broader range of applications.Traditional plasticizers decrease the low-temperature performance of PVCcompounds with increasing polarity or increased viscosity of theplasticizer (see Plastics Additives Handbook, 4^(th) Ed., Edited byGachter and Muller, Hanser/Gardner Publications, Inc., Cincinnati, Ohio,1993). Unexpectedly it has been found that high molecular weight PHAcopolymers or copolymer blends improves the low temperature flexibilityof PVC. “Non-extractable” refers to the inability of the PHA to beremoved from the PVC/PHA blend by contact with a solvent, exposure tohigh heat or even by molecular diffusion out of the blend as mostplasticizers are prone to at room temperature or use conditions.

It has also been found that when the PHA is branched or crosslinked byreactive extrusion prior to addition to rigid PVC, the PHA greatlyimproves the impact strength of the PVC without causing a significantdecrease in other properties such as tensile strength, modulus,dimensional stability and die swell as is typically observed when otherimpact modifiers are utilized. For example, an improvement in NotchedIzod Impact strength can be observed in branched PHA/PVC blends of 30%,40%, 50%, 60% or 70% greater as compared to non-crosslinked PHA/PVCblends.

The PHAs themselves include homopolymers (excludingpoly-3-hydroxybutyrate at 100% of the composition), copolymers(excluding poly 3-hydroxybutyrate-3-hydroxyvalerate at 100%) or blendedPHAs. The fully amorphous PHAs (having low percent crystallinity (<10%)and sometimes no observed melting point temperature) have propertiesthat are consistent with rubbery polymers where they are extremelyflexible at room temperature. The mostly amorphous or rubber phase PHAsincludes polymers and copolymers of 4-hydroxybutyrate,3-hydroxyhexanoate, 6-hydroxyhexanoate, 5-hydroxyvalerate or3-hydroxyoctanoate, and combinations thereof but do not include only100% P3HB or P3HB-co-3HV are included in certain embodiments. Theresultant PHA for combining with the PVC, PMMA or POM resins may be ablend, copolymer, mixture or combination of one, two or three or morePHA components wherein one of the components is an amorphous or rubberyphase material. The crystallinity of polymers, which fundamentallyaffects all of its physical properties, can be measured using a numberof techniques such as differential scanning calorimetry (DSC), X-raydiffraction (XRD) or overall density. For the DSC method, a sample ofunknown crystallinity is first thermally condition and then heated inthe DSC beyond its melting point. The data obtained from the DSC on thesample is heat flow vs. temperature. The heat of melting (ΔH_(m)) isthen measured (J/g) by integrating the area under the melting peak forthe sample. To obtain the percent crystallinity of the unknown sample,its heat of melting is divided by the heat melting for the same orsimilar material of known crystallinity (values are published in theliterature) and multiplied by 100%. This value then is an estimate ofthe percent crystallinity of the unknown material.

Pure P4HB homopolymer is a fully flexible (mostly amorphous), rubberypolymer at room temperature with a significantly lower glass transitiontemperature (T_(g)=−48 to −43° C.) than that of pure P3HB (T_(g)=12 to15° C.). When it is combined with 3-hydroxybutyrate in a copolymer,where the % 4HB>25% by weight, the copolymer retains its rubberyproperties (T_(g)=−15° C. to −45° C.) as described by C. Cong et. al.,Journal of Applied Polymer Science, vol. 109, p 1962, 2008. If therubbery PHA copolymer is blended with other polymers, it readily forms aseparate rubbery phase which imparts a toughening effect on the overallpolymer blend. Because of this property and its proven biodegradabilityin various environments, it is a beneficial material for improving thetoughness, tear and impact properties of PVC, PMMA and POM polymerresins.

The PVCs tensile properties are modified by blending with the PHAs.Combining (e.g., mixing or blending) the PVC and PHA provides thefollowing benefits compared to PVC without PHA such as: (1) highertensile elongation (2) higher tensile toughness and (3) improved thermalstability and/or better melt stability, resulting in a broaderprocessing window for the overall composition and subsequentapplications of these compositions in production of articles, films andthe like.

The temperatures experienced by a polymer during processing can cause adrop in melt strength due to thermal degradation, which can in turncause difficulties in processing the polymer(s). Increased melt strengthis therefore useful in that it allows the polymers to be processedacross a broader temperature range. A broader “processing window” isespecially beneficial in certain polymer applications, such as in theproduction of blown film (i.e., in preventing or reducing bubblecollapse), or cast film extrusion, thermoformed articles (i.e.,preventing or reducing sheet sag during thermoforming), profile extrudedarticles (i.e., preventing or reducing sag), non-woven fibers,monofilament, etc. Additionally, articles made from the compositionsdescribed herein exhibit greater tensile toughness and elongation whilemaintaining biodegradability. The increases in tensile toughness can be10 to 40 fold greater. The increases in elongation can be 10 to 60 foldgreater. Tensile toughness increase can be 10-20, 20-30 or 25-35 fold.Elongation increase can be 20-30, 30-40 or 45-60 fold.

Increased melt strength is useful in that it allows the polymers to beformed under a broader temperature range when the polymer is processed.The polymer melt at processing temperatures and can cause difficultiesin forming these polymers into products. Additionally, the improvementshown in films made from the methods are compositions described hereinare greater tensile strength, tear resistance and greater punctureresistance.

The films produced by the compositions described herein can also be usedto make laminates. The biodegradable laminates comprising thecompositions of the invention are suitable for coating other layers suchas paper to produce articles or containers. The laminate is produced forexample by co-extruding a composition of the invention onto a paperlayer or with another thermoplastic blend or composition. Other layersof thermoplastic polymers or additional layers of a composition of theinvention can also be included or stacked to form laminates. Forexample, adhesive layers can also be added or other polymer layers thatimpart particular desired properties. For example, the blended materialsor laminates can be different and improved by varying compositions tochange the degree of hardness, softness, flexibility, tackiness,toughness, ductility, processability, opaqueness and the like.Additives, such as inorganic fillers, anti-blocking agents, plasticizersand the like are also contemplated.

In certain aspects, the laminate can be 1 to 15 layers, for example 2layers, 3 layers, 4 layers or 5 layers, 6 layers, 7 layers, 8 layers, 10layers, 11 layers, 12 layers, 13 layers, 14 layers or 15 layers. Theoverall size of the laminate is about 10 microns to about 100 microns,for example 10-50 microns, 20-60 microns, 25-75 microns. Each individuallayer can be about 1 to about 2 microns, for example about 1 to about 5micron, about 2 to about 4 microns, about 2 to about 5 microns. For eachlaminate, at least one layer is a composition of the invention, forexample, the composition of the first, second, third or fourth aspect ofthe invention. In certain embodiments, the compositions of the inventioncomprise more than one layer, for example two, three, four or more.

The methods and branched compositions of the invention improve the meltstrength of PHA polymer component, a desirable property for many polymerproduct applications. Melt strength is a rheological property that canbe measured a number of ways. One measure is G′ where G′ is the polymerstorage modulus measured by rotational rheometry at melt processingtemperatures.

As used herein, amorphous refers to the state of the PHA which is notcrystalline, for example, no lattice structure characteristic of acrystalline state. The degree of crystallinity for the inventiondescribed herein is the fraction of the polymer that exists in anorderly state, having a lattice structure. In certain embodiments, onephase of the multiphase PHA is between about 0 to about 5%crystallinity, for example the degree of crystallinity in percent isabout 0, or is minimally observed to be less than about 1%. In apreferred embodiment, the degree of crystallinity of one phase of themultiphase PHA is below 3%, for example, below 2% or below 1% or rangesor numbers calculated between these percentages such as 2.5%. The degreeof crystallinity calculated for the compositions of the invention isminimal and can be determined by various methods, for example, densitycalculations, x-ray and electron diffraction, differential scanningcalorimetry, infrared absorption (FTIR), Raman spectroscopy and thelike.

T_(g) is the glass transition temperature or the glass-rubber transitiontemperature. It is defined as the temperature where the polymer chainsbegin coordinated molecular motions. Physically, the polymer modulusbegins to drop several orders of magnitude until the polymer finallyreaches a rubbery state.

Physical properties and rheological properties of polymeric materialsdepend on the molecular weight and distribution of the polymer.“Molecular weight” is calculated in a number of different ways. Unlessotherwise indicated, “molecular weight” refers to weight averagemolecular weight.

“Number average molecular weight” (M_(n)) represents the arithmetic meanof the distribution, and is the sum of the products of the molecularweights of each fraction, multiplied by its mole fraction(ΣN_(i)M_(i)/ΣV_(i)).

“Weight average molecular weight” (M_(w)) is the sum of the products ofthe molecular weight of each fraction, multiplied by its weight fraction(ΣN_(i)M_(i) ²/ΣN_(i)M_(i)). M_(w) is generally greater than or equal toM_(n).

The weight average molecular weight of the PHA amorphous rubber phase orthe rubber phase of the multiphase PHA used in the compositions of theinvention ranges between about 100,000 to about 2.5 million as measuredby light scattering and GPC with polystyrene standards. In certainembodiments, the average molecular weight is about 50,000; about100,000; about 125,000; about 150,000; about 175,000, about 200,000,about 250,000, about 3000,000, about 400,000, about 500,000, about600,000, about 700,000, about 800,000, about 900,000, about 1,000,000,about 1,200,000, about 1,300,000, about 1,400,000, about 1,500,000,about 1,600,000, about 1,700,000, about 1,800,000, about 1,900,000 about2,000,000 about 2,100,000 about 2,200,000 about 2,300,000, about2,400,000 about 2,500,000 g/mole.

Polyvinyl Chloride (PVC)

Polyvinylchloride (PVC) is a versatile, thermoplastic polymer that iscurrently used in the production of hundreds of consumer productsencompassing such diverse commercial markets as construction,electronics, healthcare, and other applications. At the global level,demand for PVC well exceeds 35 million tons per year making it the thirdlargest volume thermoplastic behind polyethylene and polypropylene. Thereason polyvinylchloride is so widely used to manufacture products isdue to a combination of its low cost, versatility and desirable materialproperties. Notable material properties include excellent resistance toacids, bases, aliphatic hydrocarbon solvents, oils, and oxidizingagents; good flame retardancy (self-extinguishing); good weatherabilityespecially when suitable additives are incorporated (stabile to ozoneand UV exposure); good insulating properties for low frequencyelectrical systems; good low temperature mechanical properties and PVCproducts generally have long life with concomitantly low maintenancecosts.

The versatility of PVC is due in part to its ability to accept largeamounts of additives or fillers which alter its material propertiesconsiderably leading to a wide variety of applications. It therefore canbe fabricated efficiently by calendaring, extrusion or coating into avery wide range of rigid, semi-rigid and flexible products. The rigidityof PVC can be quantified by measuring the modulus (flexural or tensile)or by measuring the hardness which is an indication of the resistance ofthe material to permanent deformation. There are several hardness scalessuch as Rockwell (R, L, M, E and K), Durometer (Shore A and D) andBarcol. The Shore D (ASTM D2240) hardness test consists of an indentorwhich is pressed into a flat ¼ inch thick sample while the materialhardness is read from a gauge (no units) attached to the indentor. Thehigher the hardness value, the more rigid and stiff a material is. Whileno one hardness test can characterize all flexible to stiff materials,it can be generally stated that Shore D hardness values of >65 reflectmaterials that are rigid while values <60 reflect materials that aresoft and flexible. The additives that are incorporated into PVC the mostby far are plasticizers which generally impart “rubber-like” propertiesto the PVC by lowering the glass transition temperature (T_(g)).Plasticizers also impart low temperature resistance to embrittlement ormechanical fracture. The compatibility or miscibility of a plasticizerwith a given polymer is its most beneficial property whereby high“compatibility” means a homogenous mixture of a plasticizer and polymerhaving optimum material properties. It should be noted that otheradditives such as heat stabilizers, UV stabilizers, impact modifiers andprocessing aids are also beneficial for optimizing the performance ofPVC formulations.

The most common plasticizers used to date to improve the flexibility ofPVC have been phthalates. Other types of plasticizers such asphosphates, adipates, azelates and sebacates are also utilized toimprove the flexibility of polyvinylchloride especially at lowtemperatures. More recently, PVC compounders have been evaluatingbiobased plasticizers as an alternative to the petroleum-derivedplasticizers in order to minimize the impact on the environment bothduring production of the plasticizer and end-of-life degradation of PVCproducts. Typical biobased PVC plasticizers include trialkyltrimellitate esters, vegetable-based esters such as hydrogenated castoroil, succinates and levulinic acid esters. The major shortcoming of anumber of these plasticizers, both petroleum-derived and biobased arethat they are low molecular weight compounds which can be extracted oreven lost through volatilization from PVC especially in elevatedtemperature applications. Loss of the plasticizer over time leads tostiffening, embrittlement and ultimately failure of the PVC part.

For rigid PVC, the addition of impact modifiers aids to improve andextend its material properties for various product applications. Themost effective PVC impact modifiers are preformed core shell particlesmade by graft polymerization of acrylates or methacrylates withbutadiene rubber and styrene (acrylate-butadiene-styrene (ABS) andmethacrylate-butadiene-styrene (MBS) impact modifiers). Due to thepresence of the butadiene rubber, these modifiers however are prone tofast oxidation and photodegradation in air (poor UV resistance). As suchthey find limited use in outdoors applications. To formulate impactresistant PVC articles for outdoors, other groups of impact modifierswere created. The most commercially important ones are the acrylicmodifiers including acrylonitrile-styrene-acrylate (ASA), and copolymersof acrylates and styrenics and chlorinated polyethylene (CPE) modifiers.Unfortunately, these modifiers cannot match the impact performance ofbutadiene containing terpolymers. It is desirable for rigid PVCcompounds to exhibit both high stiffness (high flexural modulus) andhigh notched impact resistance. However, commercially available PVCimpact modifiers do not impart all of the desired properties includingweatherability and UV stability.

Pure polyvinyl chloride without any plasticizer is a white, brittlesolid and is made by polymerization of the chloroethene monomer. Thepolymerization reaction used to prepare polyvinylchloride (PVC) is shownbelow:

A number of different processes can be used to prepare the polymerincluding emulsion, suspension and bulk polymerization methods. PVC isavailable in several different forms including solid, water-basedemulsions (latex) or solids suspensions in plasticizers (plastisols).Producers of PVC materials include Dupont (ELVAX™ PVC), Shell (Carina™PVC), Wacker (VIRMOL™ PVC) and Sumitomo (SUMILIT™ PVC).

Solid PVC resins are often characterized by a K value. This is a numbercalculated from dilute solution viscosity measurements of a polymer,used to denote degree of polymerization or molecular size. The formulafor calculating the PVC K value is given as:

$\frac{\log\left( {N_{S}/N_{0}} \right)}{c} = {\frac{75\; K^{2}}{1 + {1.5{Kc}}} + K}$where:

-   N_(S)=viscosity of the solution-   N₀=viscosity of the solvent-   c=concentration in grams per ml    The higher the K value, the higher the molecular weight of the PVC    resin and the melt viscosity.    Thermal Stability of PVC

Even though polyvinylchloride has been one of the most importantpolymeric materials over the past few decades, it is well known that thePVC has the disadvantage of having relatively low thermal stability.Thermal stability in general relates to the process whereby through hightemperature, high pressure, oxidation or mechanical stress, the longchains of a polymer begins to break and react with one another therebychanging the properties of the polymer. Since thermoplastic materialsare usually formed into products by the application of heat, pressureand/or mechanical stress, degradation can pose a serious problem forproduct performance.

For PVC, it is known that thermal degradation begins to occur at about190° C. and initially involves the stripping off of hydrogen chloride(dehydrochlorination) with the concomitant formation of conjugateddouble bonds or polyene sequences leading to discoloration of thepolymer. The polyene sequences can further react to form eithercrosslinks or cyclize to form benzene and toluene volatiles. In thepresence of oxygen, oxidation reactions can also occur leading to chainscission and molecular weight reduction. Thermal degradation thus causesboth chemical and physical changes, which then lead to some problems dueto PVC's reduced performance.

It has been found that the initiation of dehydrochlorination in PVCoccurs simultaneously on multiple positions along the polyvinylchloridebackbone chain where allyl chloride structures exist. These chlorineatoms which are adjacent to double bonds are more thermally labile thanthe corresponding hydrogen atoms and are therefore easily lost at hightemperatures. Once hydrogen chloride (HCl) is formed by this reaction,the HCl released acts to accelerate the thermal degradation process ofthe PVC polymer. To prevent thermal degradation from occurring inpolyvinylchlorides, additives such as organotin mercaptides/sulfides ormetal carboxylates are usually added. The metal carboxylates aremixtures based on salts of aliphatic (oleic) or aromatic (alkylbenzoic)carboxylic acids usually with combinations of barium/zinc orcalcium/zinc metals. These additives improve thermal stability by actingdirectly at the dehydrochlorination initation site and/or by reactingwith the free HCl generated. In the case of the metal carboxylates,reaction with HCl produces chloride salts which can also have adestabilizing effect on the PVC. Therefore co-stabilizers such aspolyols, phosphites and epoxy plasticizers are often used along with themetal carboxylates to improve initial color, transparency and long termPVC stability.

For semi-rigid and flexible polyvinylchlorides, plasticizer's are also amajor component of the overall product formulation. It has been foundthat plasticizer type, concentration and oxidative stability (formationof peroxide radicals) all affect the thermal stability of PVC. Studieson the influence of plasticizers on PVC thermal stability have suggestedthat solvation of the PVC chains by the plasticizer can have a positivethermal stabilizing effect on the PVC polymer (D. Braun, “ThermalDegradation of PolyvinylChloride” in Developments in PolymerDegradation, 1981; M. Semsarzadeh et. al., Iranian Polymer Journal, vol.14, No. 9, 769 (2005)).

Measurement of the thermal stability of PVC has been carried out by avariety of techniques. These are based on changes in color on heatingPVC test sheets (static heat test), temperature at which first weightloss for PVC occurs on heating (dynamic heat test) or the time to detectHCl when PVC is heated. For the dynamic heat test, ThermogravimetricAnalysis (TGA) can be carried out on a PVC sample where by the sample isheated under a nitrogen or oxygen atmosphere while the % weight lossversus temperature is recorded. Using TGA, the temperature at whichthermal degradation starts is defined either as the point at whichcatastrophic weight loss starts occurring (T_(onset)), or thetemperature where the percent weight loss reaches 1% or 5% of theinitial sample weight. The more thermally stable the PVC sample, thehigher the temperature where degradation is measured to start.

Polymethylmethacrylate (PMMA)

Polymethyl methacrylate is a lightweight, hard, transparentthermoplastic material that is largely used to replace glass inapplications such as automotive, construction and electronics. Theglobal demand for PMMA is predicted to reach 2.9 million metric tons bythe year 2015 with the largest growth to occur in the Asia-Pacificsector. PMMA is also considered an economical alternative topolycarbonate in applications where extreme strength is not required. Itis often preferred because of its moderate properties, ease ofprocessing and its low cost. Additionally PMMA has good compatibilitywith human tissue and is used to replace intraocular lenses in the eye,as contact lens material, bone cement and dental filling materials.

PMMA is synthesized via emulsion, solution or bulk polymerizationtypically using a radical initiator. All commercial PMMA material isatactic in structure and completely amorphous with a T_(g)˜105° C. Thechemical structure of the methylmethacrylate monomer is shown below:

PMMA can be processed by injection molding, extrusion, thermoforming andmonomer casting. Even though PMMA is known to swell and dissolve in manyorganic solvents and has poor resistance to many other chemicals onaccount of its easily hydrolyzed ester groups, its environmentalstability is superior to that of most other plastics such as polystyreneand polyethylene, and PMMA is therefore often the material of choice foroutdoor applications. PMMA is sold under the tradenames LUCITE™,PLEXIGLAS™, PERSPEX™ and OPTIX™.

Due to the brittleness and low impact strength ofpolymethylmethacrylate, in most applications PMMA is modified to improveits thermal and mechanical properties. Modification schemes includecopolymerizing MMA monomer with butyl acrylates to improve impactstrength; copolymerizing with methacrylic acid to increase T_(g); addingplasticizers to PMMA to improve impact properties (which has the effectof lowering T_(g)) and adding fillers or other modifiers.

Polyoxymethylene (POM)

Polyoxymethylene is a simple polyether polymer (also known as acetal)that is produced by the polymerization of anhydrous formaldehyde usinganionic catalysts. The resulting polymer is then stabilized by reactionwith acetic anhydride to endcap the polymer chains preventing them fromdepolymerizing during thermal processing. The polymer repeat unitstructure for POM is shown below:

The simple repeat unit structure of POM imparts a high crystallinity tothe polymer (75-80%) making the stiffness, hardness and strength amongthe highest of all thermoplastics. The high density (1.41-1.42 g/cm3)also reflects the tight packing of the crystallized polymer chains.Interestingly, while the melt temperature of POM is rather high (175°C.), the glass transition temperature as compared to other crystallineengineering plastics is very low (−75° C.). Other properties which makethis polymer outstanding include creep and fatigue resistance, goodtoughness, high heat resistance, low coefficient of friction, low waterabsorption as well as good chemical resistance to most organic solvents.

Applications for POM resins generally include relatively small partsthat must perform a mechanical function requiring close dimensionaltolerances and good wear resistance. Automotive applications thereforeinclude gears, bearings, slides, cams and ratches. Due to its resistanceto gasoline, the use of POM for carburetor and fuel pump parts is alsocommon. The consumer electronic industry is also a large user ofpolyoxymethylene resins due to its good dielectric and electricalproperties.

POM resins are processed primarily by injection molding, rotational andblow molding (small pressure containers) and extrusion. Extrusion isused to produce semi-finished products such as rods, bars and sheetstock from which prototype parts can then be machined Commercial tradenames for POM resins include DELRIN™, KEPITAL™ and HOSTAFORM™.

Strategies for modifying the impact strength of POM include blendingthermoplastic elastomeric polyurethanes (TPU) and modification of thePOM backbone by incorporation of comonomers such as diols such asethylene glycol and 1,4-butandiol.

Polyhydroxyalkanoates (PHAs)

Polyhydroxyalkanoates (PHA's) are biological polyesters synthesized by abroad range of natural and genetically engineered bacteria as well asgenetically engineered plant crops (Braunegg et al., (1998), JBiotechnology 65:127-161; Madison and Huisman, 1999, Microbiology andMolecular Biology Reviews, 63:21-53; Poirier, 2002, Progress in LipidResearch 41:131-155). These polymers are biodegradable thermoplasticmaterials, produced from renewable resources, with the potential for usein a broad range of industrial applications (Williams & Peoples,CHEMTECH 26:38-44 (1996)).

Useful microbial strains for producing PHAs, include Alcaligeneseutrophus (renamed as Ralstonia eutropha), Alcaligenes latus,Azotobacter, Aeromonas, Comamonas, Pseudomonads, and geneticallyengineered organisms including genetically engineered microbes such asPseudomonas, Ralstonia and Escherichia coli.

In general, a PHA is formed by enzymatic polymerization of one or moremonomer units inside a living cell. Over 100 different types of monomershave been incorporated into the PHA polymers (Steinbüchel and Valentin,1995, FEMS Microbiol. Lett. 128:219-228. Examples of monomer unitsincorporated in PHAs for this invention include 2-hydroxybutyrate,glycolic acid, 3-hydroxybutyrate (hereinafter referred to as 3HB),3-hydroxypropionate (hereinafter referred to as 3HP), 3-hydroxyvalerate(hereinafter referred to as 3HV), 3-hydroxyhexanoate (hereinafterreferred to as 3HH), 3-hydroxyheptanoate (hereinafter referred to as3HH), 3-hydroxyoctanoate (hereinafter referred to as 3HO),3-hydroxynonanoate (hereinafter referred to as 3HN), 3-hydroxydecanoate(hereinafter referred to as 3HD), 3-hydroxydodecanoate (hereinafterreferred to as 3HDd), 4-hydroxybutyrate (hereinafter referred to as4HB), 4-hydroxyvalerate (hereinafter referred to as 4HV),5-hydroxyvalerate (hereinafter referred to as 5HV), and6-hydroxyhexanoate (hereinafter referred to as 6HH). 3-hydroxyacidmonomers incorporated into PHAs are the (D) or (R) 3-hydroxyacid isomerwith the exception of 3HP which does not have a chiral center. Forcompositions included herein, the PHA composition does not includepoly(lactic acid).

In some embodiments, the PHA in the methods described herein is ahomopolymer (where all monomer units are the same). Examples of PHAhomopolymers include poly 3-hydroxyalkanoates (e.g., poly3-hydroxypropionate (hereinafter referred to as P3HP), poly3-hydroxybutyrate (hereinafter referred to as P3HB) and poly3-hydroxyvalerate), poly 4-hydroxyalkanoates (e.g., poly4-hydroxybutyrate (hereinafter referred to as P4HB), or poly4-hydroxyvalerate (hereinafter referred to as P4HV)) and poly5-hydroxyalkanoates (e.g., poly 5-hydroxyvalerate (hereinafter referredto as P5HV)).

In certain embodiments, the starting PHA can be a copolymer (containingtwo or more different monomer units) in which the different monomers arerandomly distributed in the polymer chain. Examples of PHA copolymersinclude poly 3-hydroxybutyrate-co-3-hydroxypropionate (hereinafterreferred to as PHB3HP), poly 3-hydroxybutyrate-co-4-hydroxybutyrate(hereinafter referred to as P3HB4HB), poly3-hydroxybutyrate-co-4-hydroxyvalerate (hereinafter referred to asPHB4HV), poly 3-hydroxybutyrate-co-3-hydroxyvalerate (hereinafterreferred to as PHB3HV), poly 3-hydroxybutyrate-co-3-hydroxyhexanoate(hereinafter referred to as PHB3HH) and poly3-hydroxybutyrate-co-5-hydroxyvalerate (hereinafter referred to asPHB5HV).

By selecting the monomer types and controlling the ratios of the monomerunits in a given PHA copolymer a wide range of material properties canbe achieved. Although examples of PHA copolymers having two differentmonomer units have been provided, the PHA can have more than twodifferent monomer units (e.g., three different monomer units, fourdifferent monomer units, five different monomer units, six differentmonomer units) An example of a PHA having 4 different monomer unitswould be PHB-co-3HH-co-3HO-co-3HD or PHB-co-3-HO-co-3HD-co-3HDd (thesetypes of PHA copolymers are hereinafter referred to as PHB3HX).Typically where the PHB3HX has 3 or more monomer units the 3HB monomeris at least 70% by weight of the total monomers, preferably 85% byweight of the total monomers, most preferably greater than 90% by weightof the total monomers for example 92%, 93%, 94%, 95%, 96% by weight ofthe copolymer and the HX comprises one or more monomers selected from3HH, 3HO, 3HD, 3HDd.

The homopolymer (where all monomer units are identical) P3HB and3-hydroxybutyrate copolymers (P3HB3HP, P3HB4HB, P3HB3HV, P3HB4HV,P3HB5HV, P3HB3HHP, hereinafter referred to as PHB copolymers) containing3-hydroxybutyrate and at least one other monomer are of particularinterest for commercial production and applications. It is useful todescribe these copolymers by reference to their material properties asfollows. Type 1 PHB copolymers typically have a glass transitiontemperature (Tg) in the range of 6° C. to −10° C., and a meltingtemperature T_(m) of between 80° C. to 180° C. Type 2 PHB copolymerstypically have a Tg of −20° C. to −50° C. and Tm of 55° C. to 90° C. Inparticular embodiments, the Type 2 copolymer has a mostly amorphousphase with a T_(g) of −15° C. to −45° C.

Preferred Type 1 PHB copolymers have two monomer units with a majorityof their monomer units being 3-hydroxybutyrate monomer by weight in thecopolymer, for example, greater than 78% 3-hydroxybutyrate monomer.Preferred PHB copolymers for this invention are biologically producedfrom renewable resources and are selected from the following group ofPHB copolymers:

PHB3HV is a Type 1 PHB copolymer where the 3HV content is in the rangeof 3% to 22% by weight of the polymer and preferably in the range of 4%to 15% by weight of the copolymer for example: 4% 3HV; 5% 3HV; 6% 3HV;7% 3HV; 8% 3HV; 9% 3HV; 10% 3HV; 11% 3HV; 12% 3HV; 13% 3HV; 14% 3HV; 15%3HV;

PHB3HP is a Type 1 PHB copolymer where the 3HP content is in the rangeof 3% to 15% by weight of the copolymer and preferably in the range of4% to 15% by weight of the copolymer for example: 4% 3HP; 5% 3HP; 6%3HP; 7% 3HP; 8% 3HP; 9% 3HP; 10% 3HP; 11% 3HP; 12% 3HP. 13% 3HP; 14%3HP; 15% 3HP.

PHB4HB is a Type 1 PHB copolymer where the 4HB content is in the rangeof 3% to 15% by weight of the copolymer and preferably in the range of4% to 15% by weight of the copolymer for example: 4% 4HB; 5% 4HB; 6%4HB; 7% 4HB; 8% 4HB; 9% 4HB; 10% 4HB; 11% 4HB; 12% 4HB; 13% 4HB; 14%4HB; 15% 4HB.

PHB4HV is a Type 1 PHB copolymer where the 4HV content is in the rangeof 3% to 15% by weight of the copolymer and preferably in the range of4% to 15% by weight of the copolymer for example: 4% 4HV; 5% 4HV; 6%4HV; 7% 4HV; 8% 4HV; 9% 4HV; 10% 4HV; 11% 4HV; 12% 4HV; 13% 4HV; 14%4HV; 15% 4HV.

PHB5HV is a Type 1 PHB copolymer where the 5HV content is in the rangeof 3% to 15% by weight of the copolymer and preferably in the range of4% to 15% by weight of the copolymer for example: 4% 5HV; 5% 5HV; 6%5HV; 7% 5HV; 8% 5HV; 9% 5HV; 10% 5HV; 11% 5HV; 12% 5HV; 13% 5HV; 14%5HV; 15% 5HV.

PHB3HH is a Type 1 PHB copolymer where the 3HH content is in the rangeof 3% to 15% by weight of the copolymer and preferably in the range of4% to 15% by weight of the copolymer for example: 4% 3HH; 5% 3HH; 6%3HH; 7% 3HH; 8% 3HH; 9% 3HH; 10% 3HH; 11% 3HH; 12% 3HH; 13% 3HH; 14%3HH; 15% 3HH;

PHB3HX is a Type 1 PHB copolymer where the 3HX content is comprised of 2or more monomers selected from 3HH, 3HO, 3HD and 3HDd and the 3HXcontent is in the range of 3% to 12% by weight of the copolymer andpreferably in the range of 4% to 10% by weight of the copolymer forexample: 4% 3HX; 5% 3HX; 6% 3HX; 7% 3HX; 8% 3HX; 9% 3HX; 10% 3HX byweight of the copolymer.

Type 2 PHB copolymers have a 3HB content of between 80% and 5% by weightof the copolymer, for example 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%,40%, 35%, 30%, 25%, 20%, 15%, 10%, 5% by weight of the copolymer.

PHB4HB is a Type 2 PHB copolymer where the 4HB content is in the rangeof 25% to 95% by weight of the copolymer and preferably in the range of35 to 75% by weight of the copolymer for example: 25% 4HB; 30% 4HB; 35%4HB; 40% 4HB; 45% 4HB; 50% 4HB; 60% 4HB; 70% 4HB; 80% 4HB; 90% 4HB and95% 4HB by weight of the copolymer.

PHB5HV is a Type 2 PHB copolymer where the 5HV content is in the rangeof 25% to 95% by weight of the copolymer and preferably in the range of35% to 75% by weight of the copolymer for example: 25% 5HV; 30% 5HV; 35%5HV; 40% 5HV; 45% 5HV; 50% 5HV by weight of the copolymer.

PHB3HH is a Type 2 PHB copolymer where the 3HH is in the range of 35% to95% by weight of the copolymer and preferably in the range of 40% to 80%by weight of the copolymer for example: 40% 3HH; 45% 3HH; 50% 3HH; 55%3HH, 60% 3HH; 65% 3HH; 70% 3HH; 75% 3HH; 80% 3HH by weight of thecopolymer.

PHB3HX is a Type 2 PHB copolymer where the 3HX content is comprised of 2or more monomers selected from 3HH, 3HO, 3HD and 3HDd and the 3HXcontent is in the range of 30% to 95% by weight of the copolymer andpreferably in the range of 35% to 90% by weight of the copolymer forexample: 35% 3HX; 40% 3HX; 45% 3HX; 50% 3HX; 55% 3HX 60% 3HX; 65% 3HX;70% 3HX; 75% 3HX; 80% 3HX; 85% 3HX; 90% 3HX by weight of the copolymer.

PHAs for use in the methods, compositions and pellets described in thisinvention are selected from: PHB or a Type 1 PHB copolymer; a PHA blendof PHB with a Type 1 PHB copolymer where the PHB content by weight ofPHA in the PHA blend is in the range of 5% to 95% by weight of the PHAin the PHA blend; a PHA blend of PHB with a Type 2 PHB copolymer wherethe PHB content by weight of the PHA in the PHA blend is in the range of5% to 95% by weight of the PHA in the PHA blend; a PHA blend of a Type 1PHB copolymer with a different Type 1 PHB copolymer and where thecontent of the first Type 1 PHB copolymer is in the range of 5% to 95%by weight of the PHA in the PHA blend; a PHA blend of a Type 1 PHBcopolymer with a Type 2 PHA copolymer where the content of the Type 1PHB copolymer is in the range of 30% to 95% by weight of the PHA in thePHA blend; a PHA blend of PHB with a Type 1 PHB copolymer and a Type 2PHB copolymer where the PHB content is in the range of 10% to 90% byweight of the PHA in the PHA blend, where the Type 1 PHB copolymercontent is in the range of 5% to 90% by weight of the PHA in the PHAblend and where the Type 2 PHB copolymer content is in the range of 5%to 90% by weight of the PHA in the PHA blend.

The PHA blend of PHB with a Type 1 PHB copolymer is a blend of PHB withPHB3HP where the PHB content in the PHA blend is in the range of 5% to90% by weight of the PHA in the PHA blend and the 3HP content in thePHB3HP is in the range of 7% to 15% by weight of the PHB3HP.

The PHA blend of PHB with a Type 1 PHB copolymer is a blend of PHB withPHB3HV where the PHB content of the PHA blend is in the range of 5% to90% by weight of the PHA in the PHA blend and the 3HV content in thePHB3HV is in the range of 4% to 22% by weight of the PHB3HV.

The PHA blend of PHB with a Type 1 PHB copolymer is a blend of PHB withPHB4HB where the PHB content of the PHA blend is in the range of 5% to90% by weight of the PHA in the PHA blend and the 4HB content in thePHB4HB is in the range of 4% to 15% by weight of the PHB4HB.

The PHA blend of PHB with a Type 1 PHB copolymer is a blend of PHB withPHB4HV where the PHB content of the PHA blend is in the range of 5% to90% by weight of the PHA in the PHA blend and the 4HV content in thePHB4HV is in the range of 4% to 15% by weight of the PHB4HV.

The PHA blend of PHB with a Type 1 PHB copolymer is a blend of PHB withPHB5HV where the PHB content of the PHA blend is in the range of 5% to90% by weight of the PHA in the PHA blend and the 5HV content in thePHB5HV is in the range of 4% to 15% by weight of the PHB5HV.

The PHA blend of PHB with a Type 1 PHB copolymer is a blend of PHB withPHB3HH where the PHB content of the PHA blend is in the range of 5% to90% by weight of the PHA in the PHA blend and the 3HH content in thePHB3HH is in the range of 4% to 15% by weight of the PHB3HH.

The PHA blend of PHB with a Type 1 PHB copolymer is a blend of PHB withPHB3HX where the PHB content of the PHA blend is in the range of 5% to90% by weight of the PHA in the PHA blend and the 3HX content in thePHB3HX is in the range of 4% to 15% by weight of the PHB3HX.

The PHA blend is a blend of a Type 1 PHB copolymer selected from thegroup PHB3HV, PHB3HP, PHB4HB, PHBV, PHV4HV, PHB5HV, PHB3HH and PHB3HXwith a second Type 1 PHB copolymer which is different from the firstType 1 PHB copolymer and is selected from the group PHB3HV, PHB3HP,PHB4HB, PHBV, PHV4HV, PHB5HV, PHB3HH and PHB3HX where the content of theFirst Type 1 PHB copolymer in the PHA blend is in the range of 10% to90% by weight of the total PHA in the blend.

The PHA blend of PHB with a Type 2 PHB copolymer is a blend of PHB withPHB4HB where the PHB content in the PHA blend is in the range of 30% to95% by weight of the PHA in the PHA blend and the 4HB content in thePHB4HB is in the range of 20% to 60% by weight of the PHB4HB.

The PHA blend of PHB with a Type 2 PHB copolymer is a blend of PHB withPHB5HV where the PHB content in the PHA blend is in the range of 30% to95% by weight of the PHA in the PHA blend and the 5HV content in thePHB5HV is in the range of 20% to 60% by weight of the PHB5HV.

The PHA blend of PHB with a Type 2 PHB copolymer is a blend of PHB withPHB3HH where the PHB content in the PHA blend is in the range of 35% to95% by weight of the PHA in the PHA blend and the 3HH content in thePHB3HH is in the range of 35% to 90% by weight of the PHB3HX.

The PHA blend of PHB with a Type 2 PHB copolymer is a blend of PHB withPHB3HX where the PHB content in the PHA blend is in the range of 30% to95% by weight of the PHA in the PHA blend and the 3HX content in thePHB3HX is in the range of 35% to 90% by weight of the PHB3HX.

The PHA blend is a blend of PHB with a Type 1 PHB copolymer and a Type 2PHB copolymer where the PHB content in the PHA blend is in the range of10% to 90% by weight of the PHA in the PHA blend, the Type 1 PHBcopolymer content of the PHA blend is in the range of 5% to 90% byweight of the PHA in the PHA blend and the Type 2 PHB copolymer contentin the PHA blend is in the range of 5% to 90% by weight of the PHA inthe PHA blend.

For example, a PHA blend can have a PHB content in the PHA blend in therange of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HVcontent in the PHA blend in the range 5% to 90% by weight of the PHA inthe PHA blend, where the 3HV content in the PHB3HV is in the range of 3%to 22% by weight of the PHB3HV, and a PHBHX content in the PHA blend inthe range of 5% to 90% by weight of the PHA in the PHA blend where the3HX content in the PHBHX is in the range of 35% to 90% by weight of thePHBHX.

For example, a PHA blend can have a PHB content in the PHA blend in therange of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HVcontent in the PHA blend in the range 5% to 90% by weight of the PHA inthe PHA blend, where the 3HV content in the PHB3HV is in the range of 3%to 22% by weight of the PHB3HV, and a PHB4HB content in the PHA blend inthe range of 5% to 90% by weight of the PHA in the PHA blend where the4HB content in the PHB4HB is in the range of 20% to 60% by weight of thePHB4HB.

For example, a PHA blend can have a PHB content in the PHA blend in therange of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HVcontent in the PHA blend in the range 5% to 90% by weight of the PHA inthe PHA blend, where the 3HV content in the PHB3HV is in the range of 3%to 22% by weight of the PHB3HV, and a PHB5HV content in the PHA blend inthe range of 5% to 90% by weight of the PHA in the PHA blend where the5HV content in the PHB5HV is in the range of 20% to 60% by weight of thePHB5HV.

For example, a PHA blend can have a PHB content in the PHA blend in therange of 10% to 90% by weight of the PHA in the PHA blend, a PHB4HBcontent in the PHA blend in the range 5% to 90% by weight of the PHA inthe PHA blend, where the 4HB content in the PHB4HB is in the range of 4%to 15% by weight of the PHB4HB, and a PHB4HB content in the PHA blend inthe range of 5% to 90% by weight of the PHA in the PHA blend where the4HB content in the PHB4HB is in the range of 20% to 60% by weight of thePHB4HB.

For example, a PHA blend can have a PHB content in the PHA blend in therange of 10% to 90% by weight of the PHA in the PHA blend, a PHB4HBcontent in the PHA blend in the range 5% to 90% by weight of the PHA inthe PHA blend, where the 4HB content in the PHB4HB is in the range of 4%to 15% by weight of the PHB4HB, and a PHB5HV content in the PHA blend inthe range of 5% to 90% by weight of the PHA in the PHA blend and wherethe 5HV content in the PHB5HV is in the range of 30% to 90% by weight ofthe PHB5HV.

For example, a PHA blend can have a PHB content in the PHA blend in therange of 10% to 90% by weight of the PHA in the PHA blend, a PHB4HBcontent in the PHA blend in the range 5% to 90% by weight of the PHA inthe PHA blend, where the 4HB content in the PHB4HB is in the range of 4%to 15% by weight of the PHB4HB, and a PHB3HX content in the PHA blend inthe range of 5% to 90% by weight of the PHA in the PHA blend and wherethe 3HX content in the PHB3HX is in the range of 35% to 90% by weight ofthe PHB3HX.

For example, a PHA blend can have a PHB content in the PHA blend in therange of 10% to 90% by weight of the PHA in the PHA blend, a PHB4HVcontent in the PHA blend in the range 5% to 90% by weight of the PHA inthe PHA blend, where the 4HV content in the PHB4HV is in the range of 3%to 15% by weight of the PHB4HV, and a PHB5HV content in the PHA blend inthe range of 5% to 90% by weight of the PHA in the PHA blend where the5HV content in the PHB5HV is in the range of 30% to 90% by weight of thePHB5HV.

For example, a PHA blend can have a PHB content in the PHA blend in therange of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HHcontent in the PHA blend in the range 5% to 90% by weight of the PHA inthe PHA blend, where the 3HH content in the PHB3HH is in the range of 3%to 15% by weight of the PHB3HH, and a PHB4HB content in the PHA blend inthe range of 5% to 90% by weight of the PHA in the PHA blend where the4HB content in the PHB4HB is in the range of 20% to 60% by weight of thePHB4HB.

For example, a PHA blend can have a PHB content in the PHA blend in therange of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HHcontent in the PHA blend in the range 5% to 90% by weight of the PHA inthe PHA blend, where the 3HH content in the PHB3HH is in the range of 3%to 15% by weight of the PHB3HH, and a PHB5HV content in the PHA blend inthe range of 5% to 90% by weight of the PHA in the PHA blend where the5HV content in the PHB5HV is in the range of 20% to 60% by weight of thePHB5HV.

For example, a PHA blend can have a PHB content in the PHA blend in therange of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HHcontent in the PHA blend in the range 5% to 90% by weight of the PHA inthe PHA blend, where the 3HH content in the PHB3HH is in the range of 3%to 15% by weight of the PHB3HH, and a PHB3HX content in the PHA blend inthe range of 5% to 90% by weight of the PHA in the PHA blend where the3HX content in the PHB3HX is in the range of 35% to 90% by weight of thePHB3HX.

For example, a PHA blend can have a PHB content in the PHA blend in therange of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HXcontent in the PHA blend in the range 5% to 90% by weight of the PHA inthe PHA blend, where the 3HX content in the PHB3HX is in the range of 3%to 12% by weight of the PHB3HX, and a PHB3HX content in the PHA blend inthe range of 5% to 90% by weight of the PHA in the PHA blend where the3HX content in the PHB3HX is in the range of 35% to 90% by weight of thePHB3HX.

For example, a PHA blend can have a PHB content in the PHA blend in therange of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HXcontent in the PHA blend in the range 5% to 90% by weight of the PHA inthe PHA blend, where the 3HX content in the PHB3HX is in the range of 3%to 12% by weight of the PHB3HX, and a PHB4HB content in the PHA blend inthe range of 5% to 90% by weight of the PHA in the PHA blend where the4HB content in the PHB4HB is in the range of 20% to 60% by weight of thePHB4HB.

For example, a PHA blend can have a PHB content in the PHA blend in therange of 10% to 90% by weight of the PHA in the PHA blend, a PHB3HXcontent in the PHA blend in the range 5% to 90% by weight of the PHA inthe PHA blend, where the 3HX content in the PHB3HX is in the range of 3%to 12% by weight of the PHB3HX, and a PHB5HV content in the PHA blend inthe range of 5% to 90% by weight of the PHA in the PHA blend where the5HV content in the PHB5HV is in the range of 20% to 60% by weight of thePHB5HV.

The PHA blend is a blend as disclosed in U.S. Published Application No.US 2004/0220355, by Whitehouse, published Nov. 4, 2004, which isincorporated herein by reference in its entirety.

Microbial systems for producing the PHB copolymer PHBV are disclosed in,e.g., U.S. Pat. No. 4,477,654 to Holmes, which is incorporated herein byreference in its entirety. U.S. Published Application No. US2002/0164729 (also incorporated herein by reference in its entirety) bySkraly and Sholl describes useful systems for producing the PHBcopolymer PHB4HB. Useful processes for producing the PHB copolymerPHB3HH have been described (Lee et al., 2000, Biotechnology andBioengineering 67:240-244; Park et al., 2001, Biomacromolecules2:248-254). Processes for producing the PHB copolymers PHB3HX have beendescribed by Matsusaki et al. (Biomacromolecules 2000, 1:17-22).Genetically engineered microbial PHA production system with fast growinghosts such as Escherichia coli have been developed. In certainembodiments, genetic engineering also allows for the modification ofwild-type microbes to improve the production of the 4HB comonomer.Examples of PHA production modification are described in Steinbuchel et.al., FEMS Microbiol. Lett., 1995, 128, p 218. PCT Publication No. WO98/04713 describes methods for controlling the molecular weight usinggenetic engineering to control the level of the PHA synthase enzyme.Commercially useful strains, including Alcaligenes eutrophus (renamed asRalstonia eutropha), Alcaligenes latus, Azotobacter vinlandii, andPseudomonads for producing PHA's are disclosed in Lee, Biotechnology &Bioengineering, 1994, 49:p1 and Braunegg et. al., J Biotechnology 1998,65, p 127. U.S. Pat. Nos. 6,316,262; 7,229,804; 6,759,219 and 6,689,589describe biological systems for manufacture of PHA polymers containing4-hydroxyacids are incorporated herein by reference. Also incorporatedby reference is PCT Publication No. WO 2010/068953 which describesmicrobial production of poly-3-hydroxybutyrate-co-5-hydroxyvaleratecopolymers.

In determining the molecular weight techniques such as gel permeationchromatography (GPC) can be used. In the methodology, a polystyrenestandard is utilized. The PHA can have a polystyrene equivalent weightaverage molecular weight (in daltons) of at least 500, at least 10,000,or at least 50,000 and/or less than 2,000,000, less than 1,000,000, lessthan 1,500,000, and less than 800,000. In certain embodiments,preferably, the PHAs generally have a weight-average molecular weight inthe range of 100,000 to 700,000. For example, the molecular weight rangefor PHB and Type 1 PHB copolymers for use in this application are in therange of 400,000 daltons to 1.5 million daltons as determined by GPCmethod and the molecular weight range for Type 2 PHB copolymers for usein the application 50,000 to 1.5 million daltons.

In certain embodiments, the PHA can have a linear equivalent weightaverage molecular weight of from about 50,000 Daltons to about 500,000Daltons and a polydispersity index of from about 2.5 to about 8.0. Asused herein, weight average molecular weight and linear equivalentweight average molecular weight are determined by gel permeationchromatography, using, e.g., chloroform as both the eluent and diluentfor the PHA samples. Calibration curves for determining molecularweights are generated using linear polystyrenes as molecular weightstandards and a ‘log MW vs. elution volume’ calibration method.

Culturing of Host to Produce PHA Biomass

In general, a recombinant host is cultured in a medium with a carbonsource and other essential nutrients to produce the PHA biomass byfermentation techniques either in batches or continuously using methodsknown in the art. Additional additives can also be included, forexample, antifoaming agents and the like for achieving desired growthconditions. Fermentation is particularly useful for large scaleproduction. An exemplary method uses bioreactors for culturing andprocessing the fermentation broth to the desired product. Othertechniques such as separation techniques can be combined withfermentation for large scale and/or continuous production.

As used herein, the term “feedstock” refers to a substance used as acarbon raw material in an industrial process. When used in reference toa culture of organisms such as microbial or algae organisms such as afermentation process with cells, the term refers to the raw materialused to supply a carbon or other energy source for the cells. Carbonsources useful for the production of PHA's include simple, inexpensivesources, for example, glucose, levoglucosan, sucrose, lactose, fructose,xylose, maltose, arabinose and the like alone or in combination. Inother embodiments, the feedstock is molasses or starch, fatty acids,vegetable oils or a lignocellulosic material and the like. It is alsopossible to use organisms to produce the P4HB biomass that grow onsynthesis gas (CO₂, CO and hydrogen) produced from renewable biomassresources and/or methane originating from landfill gas.

Introduction of particular pathway genes allows for flexibility inutilizing readily available and inexpensive feedstocks. A “renewable”feedstock refers to a renewable energy source such as material derivedfrom living organisms or their metabolic byproducts including materialderived from biomass, often consisting of underutilized components likechaff or stover. Agricultural products specifically grown for use asrenewable feedstocks include, for example, corn, soybeans, switchgrassand trees such as poplar, wheat, flaxseed and rapeseed, sugar cane andpalm oil. As renewable sources of energy and raw materials, agriculturalfeedstocks based on crops are the ultimate replacement for declining oilreserves. Plants use solar energy and carbon dioxide fixation to makethousands of complex and functional biochemicals beyond the currentcapability of modern synthetic chemistry. These include fine and bulkchemicals, pharmaceuticals, nutraceuticals, flavanoids, vitamins,perfumes, polymers, resins, oils, food additives, bio-colorants,adhesives, solvents, and lubricants.

Blends of PVC with PHA and Combinations Thereof

In certain embodiments, the polymers for use in the methods andcompositions are blended in the presence of additives (e.g., nucleatingagent(s), compatibilizer(s), thermal stabilizers, anti-slip additive(s)and the like, to form compositions with improved toughness properties.The percentages of PVC in the PVC/PHA blend are 50% to 95% by weight,for example 70-95%. In certain compositions of the invention, thepercentages of PVC and PHA of the total polymer compositions ranges fromabout 95% PVC to about 5% PHA or about 50% PVC to about 50% PHA. Forexample the PVC/PHA ratio can be 95/5, 90/10, 85/15, 80/20, 75/25,70/30, 65/35, 60/40, 55/45 or 50/50.

Thermal Stabilization of PVC/PHA Blends

The thermal degradation of PVC is governed by the following degradationreactions: dehydro chlorination, autooxidation, mechanical/chemicalchain scission and crosslinking. In commercial applications, thesedegradation mechanisms are controlled by the addition of heatstabilizers which are commonly composed of organic salts containing Na,K, Ca, Ba or Zn metals. These thermal stabilizers could accelerate thethermal degradation of the PHA polymers themselves and therefore caremust taken to choose the appropriate stabilizers which willsimultaneously minimize PVC degradation but not accelerate the thermaldegradation of the PHA.

At polymer melt processing conditions (170 to 210° C.), P3HB thermallydegrades via random chain scission with formation of carboxyl groups andvinyl crotonate ester groups through a six-membered ring esterdecomposition process. Crotonic acid could be formed as result of chainscission as well as unsaturated carbon-carbon groups. Crotonic acidbeing a weak acid, does not by itself accelerate P3HB degradationfurther. There are currently no known heat stabilizers to preventformation of the six-membered ring followed by chain scission in P3HB.Metal salts of Na, Ca and Mg have been shown to accelerate the chainscission reaction, whereas compounds containing Zn, Sn, Al were shown tohave little effect on the thermal degradation reactions (see K. J. Kim,Y. Doi, H. Abe, Polymer Degradation and Stability, 93 (2008), 776-785).P4HB is somewhat more thermally stable than P3HB and thermally degradesby a different mechanism

PVC heat stabilizers which prevent the dehydrochlorination reactioninclude the salts of strongly or moderately basic metal cations such asNa, K, Ca, Ba, Sr, Mg, Pb. They are addtionally combined with primarymetal salts, such as Zn, that participate in the chlorine displacementreactions. Suitable combinations of mixed metal stabilizers includeBa/Zn or Ca/Ba/Zn which have been shown to provide good overallstabilization, initial color and long term thermal stability of PVC. TheBa/Zn cation ratios in the salt mixtures could be in the range of about1:1 to about 10:1 and preferably of about 3:1 to about 8:1, morepreferably of about 3.5:1 and 4:1 or 5:1 to 6:1. Commercial heatstabilizers useful in the described invention include MARK® 4781a(Galata Chemicals) heat stabilizer and PLASTISTAB™ 2442 (AM Stabilizers)heat stabilizer and the like.

The salt mixtures also contain an anionic group comprising two differenttypes of carboxylic acid groups. One of the types consists of one ormore anions selected from the group of linear or branched, saturated orunsaturated aliphatic carboxylic acids. The most preferred carboxylicacids are oleic acid, neodecanoic acid and isomers of octanoic acid,such as 2-ethyl hexanoate. The second type of anion consists of one ormore aromatic carboxylic acids. The aromatic carboxylic acids aremolecules containing a phenyl ring to which the carboxylic moiety isdirectly or indirectly bonded through a saturated or unsaturatedalkylene bridge; the phenyl ring can be additionally substituted withone or more alkyl groups. The preferred aromatic carboxylic acids aresubstituted derivatives of benzoic acid; the most preferred aromaticcarboxylic acids, and in particular isopropyl benzoic acid, 4-ethylbenzoic acid, 2-methyl benzoic acid, 3-methylbenzoic acid,4-methylbenzoic acid, 3,4-dimethyl benzoic acid and 2,4,6-trimethylbenzoic acid. The presence of aromatic carboxylic acids is verybeneficial because their salts improve the initial color of the PVCformulations during processing without affecting transparency.Optionally, one or more co-stabilizers, such as β-diketones anddihydropyridines, solutions of barium carboxylate/barium carbonate(overbased barium see U.S. Pat. No. 5,656,202), zinc salts of aliphaticcarboxylic acids (to have more flexibility in the ratio Ba/Zn), organicderivatives of phosphorous and, high boiling point hydrocarbons andplasticizers used as diluents can be added to the thermal stabilizers.

Liquid thermal PVC stabilizers are generally comprised of a) a mixtureof barium and zinc salts of one or more linear or branched aliphaticsaturated or unsaturated carboxylic acids containing from 6 to 20 carbonatoms and of one or more aromatic carboxylic acid containing from 8 to10 carbon atoms, wherein the weight ratio of aliphatic acids salts toaromatic acids salts is higher than 3:1 and b) one or more organicphosphites of the formula R1OP(OR2)OR3 wherein R1, R2 and R3 are thesame or different and each is an alkyl group containing from 6 to 15carbon atoms or phenyl group or C10-C20 alkyl aryl. These types ofstabilizers are described in U.S. Pat. No. 2,294,122, European PatentNo. 0792317, U.S. Pat. No. 5,800,189 and International Patent App. No.WO2010000734A1. It has been found that the liquid type stabilizers showthe best thermal stability performance in PVC/PHA blends especially whencombined with secondary heat stabilizers such as plasticizers,antioxidants and lubricants which help to prevent thermo-oxidativedegradation. Another type of mixed metal stabilizer composition isdescribed in European Patent App. No. 0849314 A1 which consists of (A)about 10 to about 40 parts by weight of a zinc carboxylate; (B) about 50to about 80 parts by weight of an alkyl ester of thiodipropionic acid;and (C) about 5 to about 20 parts by weight of a phenolic antioxidant.

Other PVC heat stabilizers that may be used in PVC/PHA blends includemild alkalis such as sodium carbonate; various metal-free organiccompounds such as the polyols, e.g. mannitol, sorbitol, glycerol andpentaerythritol; 1,2-epoxides, e.g. soy bean oil epoxide, isooctylepoxystearate and the diglycidyl ether of2,2-bis(p-hydroxyphenyl)propane; nitrogen compounds such as phenylurea,N,N′-diphenylthiourea, and 2-phenylindole; organotin mercaptides (U.S.Pat. No. 2,641,588); mercaptoesters and thioglucolates which reportedlyimpart multifunctional stabilization (European Pat. No. 0813572);diketones complexed with metal salts of organic acids such as calciumbenzoate, 1,3-diphenylpropane-1,3-dionate (European Pat. No. 1517878);alkyl tin compounds as described in European Pat. App. No. 1877413.

Co-stabilizers such as organic phosphites are also known to impartthermal stability to chlorine-containing polymers and may also besuitable for PVC/PHA blends. These include triesters of phosphoric acidsuch as trioctyl, tridecyl, tridodecyl, tritridecyl, tripentadecyl,trioleyl, tristearyl, triphenyl, tricresyl, tris(nonylphenyl),tris(2,4-tert-butylphenyl) and tricyclohexyl phosphite (InternationalPat. No WO2005019323); phosphite compositions comprising at least two ofa tris(dibutylaryl)phosphite, a tris(monobutylaryl)phosphite, abis(dibutylaryl)monobutylaryl phosphite, and abis(monobutylaryl)dibutylaryl phosphite (U.S. Pat. No. 8,008,384);phosphite mixtures with amines to make them hydrolytically stable(European Patent App. No. 2459575).

Additives

In certain embodiments, various additives are added to the compositions.Examples of these additives include, but are not limited to,antioxidants, pigments, compatibilizers, thermal and UV stabilizers,inorganic and organic fillers, plasticizers, and optionally nucleatingagents which are not typically needed in the compositions of theinvention, anti-slip agents, anti-blocking agents and radicalscavengers. In one embodiment, inorganic fillers such as calciumcarbonate or silica are added to high rubber content PHA's (e.g. greaterthan 30% by weight 4-hydroxybutyrate content) in order to make the“rubber” PHA easier to handle and process with the PVC by reducing thesurface tack of the PHA.

In other embodiments, the compositions and methods of the inventioninclude a branching or crosslinking agent. The branching agents, alsoreferred to as free radical initiators, for use in the compositions andmethod described herein include organic peroxides which are melt blendedusing a twin screw extruder with the PHA's by a reactive extrusionprocess. Peroxides are free radical generating molecules which reactwith polymer molecules or previously branched polymers by removing ahydrogen atom from the polymer backbone, leaving behind a polymer freeradical. Polymer molecules having such radicals on their backbone arefree to combine with each other, creating branched or crosslinkedpolymer molecules. Branching agents are selected from any suitableinitiator known in the art, such as peroxides, azo-derivatives (e.g.,azo-nitriles), peresters, and peroxycarbonates. Suitable peroxides foruse in the present invention include, but are not limited to, organicperoxides, for example dialkyl organic peroxides such as2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-amylperoxy)hexane,2,5-bis(t-butylperoxy)-2,5-dimethylhexane (available from Akzo Nobel asTRIGONOX® 101), 2,5-dimethyl-di(t-butylperoxy)hexyne-3, di-t-butylperoxide, dicumyl peroxide, benzoyl peroxide, di-t-amyl peroxide,t-butylperoxy-2-ethylhexylcarbonate (Available from Akzo Nobel asTRIGONOX® 117), t-amylperoxy-2-ethylhexylcarbonate (TAEC), t-butyl cumylperoxide, n-butyl-4,4-bis(t-butylperoxy)valerate,1,1-di(t-butylperoxy)-3,3,5-trimethyl-cyclohexane,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane (CPK),1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-amylperoxy)-cyclohexane,2,2-di(t-butylperoxy)butane, ethyl-3,3-di(t-butylperoxy)butyrate,2,2-di(t-amylperoxy)propane, ethyl-3,3-di(t-amylperoxy)butyrate,t-butylperoxy-acetate, t-amylperoxyacetate, t-butylperoxybenzoate,t-amylperoxybenzoate, di-t-butyldiperoxyphthalate, and the like.Combinations and mixtures of peroxides can also be used. Examples offree radical initiators include those mentioned herein, as well as thosedescribed in, e.g., Polymer Handbook, 3^(rd) Ed., J. Brandrup & E. H.Immergut, John Wiley and Sons, 1989, Ch. 2. Irradiation (e.g., e-beam orgamma irradiation) can also be used to generate polymer branching.

As discussed above, when peroxides decompose, they form very high energyradicals that can extract a hydrogen atom from the polymer backbone.These radicals have short half-lives, thereby limiting the population ofbranched molecules that is produced during the active time period.

Cross-linking agents, also referred to as co-agents, used in the methodsand compositions of the invention are cross-linking agents comprisingtwo or more reactive functional groups such as epoxides or double bonds.These cross-linking agents modify the properties of the polymer. Theseproperties include, but are not limited to, melt strength or toughness.One type of cross-linking agent is an “epoxy functional compound.” Asused herein, “epoxy functional compound” is meant to include compoundswith two or more epoxide groups capable of increasing the melt strengthof polyhydroxyalkanoate polymers by branching, e.g., end branching asdescribed above.

When an epoxy functional compound is used as the cross-linking agent inthe disclosed methods, a branching agent is optional. As such oneembodiment of the invention is a method of branching a startingpolyhydroxyalkanoate polymer (PHA), comprising reacting a starting PHAwith an epoxy functional compound. Alternatively, the invention is amethod of branching a starting polyhydroxyalkanoate polymer, comprisingreacting a starting PHA, a branching agent and an epoxy functionalcompound. Alternatively, the invention is a method of branching astarting polyhydroxyalkanoate polymer, comprising reacting a startingPHA, and an epoxy functional compound in the absence of a branchingagent. Such epoxy functional compounds can include epoxy-functional,styrene-acrylic polymers (such as, but not limited to, e.g., JONCRYL®ADR-4368 (BASF), or MP-40 (Kaneka)), acrylic and/or polyolefincopolymers and oligomers containing glycidyl groups incorporated as sidechains (such as, but not limited to, e.g., LOTADER® (Arkema),poly(ethylene-glycidyl methacrylate-co-methacrylate)), and epoxidizedoils (such as, but not limited to, e.g., epoxidized soybean, olive,linseed, palm, peanut, coconut, seaweed, cod liver oils, or mixturesthereof, e.g., Merginat ESBO (Hobum, Hamburg, Germany) and EDENOL® B 316(Cognis, Dusseldorf, Germany)).

For example, reactive acrylics or functional acrylics cross-linkingagents are used to increase the molecular weight of the polymer in thebranched polymer compositions described herein. Such cross-linkingagents are sold commercially. BASF, for instance, sells multiplecompounds under the trade name JONCRYL®, which are described in U.S.Pat. No. 6,984,694 to Blasius et al., “Oligomeric chain extenders forprocessing, post-processing and recycling of condensation polymers,synthesis, compositions and applications,” incorporated herein byreference in its entirety. One such compound is JONCRYL® ADR-4368CS,which is styrene glycidyl methacrylate and is discussed below. Anotheris MP-40 (Kaneka). And still another is the Petra line from Honeywell,see for example, U.S. Pat. No. 5,723,730. Such polymers are often usedin plastic recycling (e.g., in recycling of polyethylene terephthalate)to increase the molecular weight (or to mimic the increase of molecularweight) of the polymer being recycled. Such polymers often have thegeneral structure:

E.I. du Pont de Nemours & Company sells multiple reactive compoundsunder the trade name ELVALOY®, which are ethylene copolymers, such asacrylate copolymers, elastomeric terpolymers, and other copolymers. Onesuch compound is ELVALOY® PTW, which is a copolymer of ethylene-n-butylacrylate and glycidyl methacrylate. Omnova sells similar compounds underthe trade names “SX64053,” “SX64055,” and “SX64056.” Other entities alsosupply such compounds commercially.

Specific polyfunctional polymeric compounds with reactive epoxyfunctional groups are the styrene-acrylic copolymers. These materialsare based on oligomers with styrene and acrylate building blocks thathave glycidyl groups incorporated as side chains. A high number of epoxygroups per oligomer chain are used, for example 5, greater than 10, orgreater than 20. These polymeric materials generally have a molecularweight greater than 3000, specifically greater than 4000, and morespecifically greater than 6000. These are commercially available fromS.C. Johnson Polymer, LLC (now owned by BASF) under the trade nameJONCRYL®, ADR 4368 material. Other types of polyfunctional polymermaterials with multiple epoxy groups are acrylic and/or polyolefincopolymers and oligomers containing glycidyl groups incorporated as sidechains. A further example of such a polyfunctional carboxy-reactivematerial is a co- or ter-polymer including units of ethylene andglycidyl methacrylate (GMA), available under the trade name LOTADER®resin, sold by Arkema. These materials can further comprise methacrylateunits that are not glycidyl. An example of this type ispoly(ethylene-glycidyl methacrylate-co-methacrylate).

Fatty acid esters or naturally occurring oils containing epoxy groups(epoxidized) can also be used. Examples of naturally occurring oils areolive oil, linseed oil, soybean oil, palm oil, peanut oil, coconut oil,seaweed oil, cod liver oil, or a mixture of these compounds. Particularpreference is given to epoxidized soybean oil (e.g., Merginat ESBO fromHobum, Hamburg; EDENOL® B 316 from Cognis, Dusseldorf; PARAPLEX® G-62from Hallstar), but others may also be used.

Other types of cross-linking agent include agents with two or moredouble bonds. Cross-linking agents with two or more double bondcross-link PHAs by after reacting at the double bonds. Examples of theseinclude: diallyl phthalate, pentaerythritol tetraacrylate,trimethylolpropane triacrylate, pentaerythritol triacrylate,dipentaerythritol pentaacrylate, diethylene glycol dimethacrylate,bis(2-methacryloxyethyl)phosphate.

In general, it appears that compounds with terminal epoxides performbetter than those with epoxide groups located elsewhere on the molecule.

Compounds having a relatively high number of end groups are the mostdesirable. Molecular weight may also play a role in this regard, andcompounds with higher numbers of end groups relative to their molecularweight (e.g., the JONCRYL®s are in the 3000-4000 g/mol range) are likelyto perform better than compounds with fewer end groups relative to theirmolecular weight (e.g., the Omnova Solutions products have molecularweights in the 100,000-800,000 g/mol range).

Additionally, polyfunctional co-agents such as divinyl benzene, triallylcyanurate and the like may be added as well. Such co-agents can be addedto one or more of these additives for easier incorporation into thepolymer. For instance, the co-agent can be mixed with a plasticizer,e.g., a non-reactive plasticizer, e.g., a citric acid ester, and thencompounded with the polymer under conditions to induce branching. Otherco-agents useful in the compositions of invention, for example,compositions of the first, second, third or fourth aspect arehyperbranched or dendritic polyesters, such as dendritic andhyperbranched acrylates those sold by Sartomer, e.g., BOLTRON™ H20.

In compositions for use in the methods and compositions describedherein, for example, plasticizers are often used to change the glasstransition temperature and modulus of the composition, but surfactantsmay also be used. Lubricants may also be used, e.g., in injectionmolding applications. Plasticizers, surfactants and lubricants may alltherefore be included in the overall composition.

In other embodiments, the compositions and methods of the inventioninclude one or more plasticizers. The plasticizers can be petroleumbased and/or biobased. Examples of plasticizers include phthaliccompounds (including, but not limited to, dimethyl phthalate, diethylphthalate, dibutyl phthalate, dihexyl phthalate, di-n-octyl phthalate,di-2-ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate,dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diundecylphthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate,dicyclohexyl phthalate, butyl benzyl phthalate, octyl decyl phthalate,butyl octyl phthalate, octyl benzyl phthalate, n-hexyl n-decylphthalate, n-octyl phthalate, and n-decyl phthalate), phosphoriccompounds (including, but not limited to, tricresyl phosphate, trioctylphosphate, triphenyl phosphate, octyl diphenyl phosphate, cresyldiphenyl phosphate, and trichloroethyl phosphate), adipic compounds(including, but not limited to, dibutoxyethoxyethyl adipate (DBEEA),dioctyl adipate, diisooctyl adipate, di-n-octyl adipate, didecyladipate, diisodecyl adipate, n-octyl n-decyl adipate, n-heptyl adipate,diisononyl and n-nonyl adipate), sebacic compounds (including, but notlimited to, dibutyl sebacate, dioctyl sebacate, diisooctyl sebacate, andbutyl benzyl sebacate), azelaic compounds, citric compounds (including,but not limited to, triethyl citrate, acetyl triethyl citrate, tributylcitrate, acetyl tributyl citrate, and acetyl trioctyl citrate), glycoliccompounds (including, but not limited to, methyl phthalyl ethylglycolate, ethyl phthalyl ethyl glycolate, and butyl phthalyl ethylglycolate), trimellitic compounds (including, but not limited to,trioctyl trimellitate and tri-n-octyl n-decyl trimellitate), phthalicisomer compounds (including, but not limited to, dioctyl isophthalateand dioctyl terephthalate), ricinoleic compounds (including, but notlimited to, methyl acetyl, recinoleate and butyl acetyl recinoleate),polyester compounds (including, but not limited to reaction products ofdiols selected from butane diol, ethylene glycol, propane 1,2 diol,propane 1,3 diol, polyethylene glycol, glycerol, diacids selected fromadipic acid, succinic acid, succinic anhydride and hydroxyacids such ashydroxystearic acid, epoxidized soy bean oil, chlorinated paraffins,chlorinated fatty acid esters, fatty acid compounds, plant oils,pigments, and acrylic compounds. The plasticizers may be used eitheralone respectively or in combinations with each other.

In certain embodiments, the compositions and methods of the inventioninclude one or more antioxidants. The antioxidants function as secondaryheat stabilizers for the PVC/PHA blends and include compounds such asalkylated monophenols, e.g., 2,6-di-tert-butyl-4-methyl-phenol;alkylthiomethylphenols, e.g., 2,4-dioctylthiomethyl-6-tert-butylphenol;alkylated hydroquinones, e.g., 2,6-di-tert-butyl-4-methoxyphenol;hydroxylated thiodiphenyl ethers, e.g.,2,2′-thiobis(6-tert-butyl-4-methylphenol); alkylidenebisphenols, e.g.,2,2′-methylenebis(6-tert-butyl-4-methylphenol); benzyl compounds, e.g.,3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether;hydroxybenzylated malonates, e.g., dioctadecyl2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate; hydroxybenzylaromatics, e.g.,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene;triazine compounds, e.g.,2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine;phosphonates and phosphonites, e.g., dimethyl2,5-di-tert-butyl-4-hydroxybenzylphosphonate; acylaminophenols, e.g.,4-hydroxylauranilide; esters ofβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid,β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid,P-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid; esters of3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydricalcohols; amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acide.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)hexamethylenediamine,vitamin E (tocopherol) and derivatives of the foregoing. Mixtures of theantioxidants may also be used.

In certain embodiments, the compositions and methods of the inventioninclude one or more surfactants. Surfactants are generally used tode-dust, lubricate, reduce surface tension, and/or densify. Examples ofsurfactants include, but are not limited to mineral oil, castor oil, andsoybean oil. One mineral oil surfactant is Drakeol 34, available fromPenreco (Dickinson, Tex., USA). Maxsperse W-6000 and W-3000 solidsurfactants are available from Chemax Polymer Additives (Piedmont, S.C.,USA). Non-ionic surfactants with HLB values ranging from about 2 toabout 16 can be used, examples being TWEEN®-20, TWEEN®-65, SPAN®-40 andSPAN®-85.

Anionic surfactants include: aliphatic carboxylic acids such as lauricacid, myristic acid, palmitic acid, stearic acid, and oleic acid; fattyacid soaps such as sodium salts or potassium salts of the abovealiphatic carboxylic acids; N-acyl-N-methylglycine salts,N-acyl-N-methyl-beta-alanine salts, N-acylglutamic acid salts,polyoxyethylene alkyl ether carboxylic acid salts, acylated peptides,alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts,naphthalenesulfonic acid salt-formalin polycondensation products,melaminesulfonic acid salt-formalin polycondensation products,dialkylsulfosuccinic acid ester salts, alkyl sulfosuccinate disalts,polyoxyethylene alkylsulfosuccinic acid disalts, alkylsulfoacetic acidsalts, (alpha-olefinsulfonic acid salts, N-acylmethyltaurine salts,sodium dimethyl 5-sulfoisophthalate, sulfated oil, higher alcoholsulfuric acid ester salts, polyoxyethylene alkyl ether sulfuric acidsalts, secondary higher alcohol ethoxysulfates, polyoxyethylene alkylphenyl ether sulfuric acid salts, monoglysulfate, sulfuric acid estersalts of fatty acid alkylolamides, polyoxyethylene alkyl etherphosphoric acid salts, polyoxyethylene alkyl phenyl ether phosphoricacid salts, alkyl phosphoric acid salts, sodium alkylamine oxidebistridecylsulfosuccinates, sodium dioctylsulfosuccinate, sodiumdihexylsulfosuccinate, sodium dicyclohexylsulfosuccinate, sodiumdiamylsulfosuccinate, sodium diisobutylsulfosuccinate, alkylamineguanidine polyoxyethanol, disodium sulfosuccinate ethoxylated alcoholhalf esters, disodium sulfosuccinate ethoxylated nonylphenol halfesters, disodium isodecylsulfosuccinate, disodiumN-octadecylsulfosuccinamide, tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinamide, disodium mono- ordidodecyldiphenyl oxide disulfonates, sodiumdiisopropylnaphthalenesulfonate, and neutralized condensed products fromsodium naphthalenesulfonate.

One or more lubricants can also be added to the compositions and methodsof the invention. Lubricants are normally used to reduce sticking to hotprocessing metal surfaces but can also act as a secondary thermalstabilizer and include polyethylene, paraffin oils, epoxidized soybeanoil and other vegetable oils, and paraffin waxes in combination withmetal stearates. Other lubricants include stearic acid, amide waxes,ester waxes, metal carboxylates, and carboxylic acids. Lubricants arenormally added to polymers in the range of about 0.1 percent to about 1percent by weight, generally from about 0.7 percent to about 0.8 percentby weight of the compound. Solid lubricants is warmed and melted beforeor during processing of the blend.

In film applications of the compositions and methods described herein,anti-block masterbatch is also added. A suitable example is a slipanti-block masterbatch mixture of erucamide (20% by weight) diatomaceousearth (15% by weight) nucleant masterbatch (3% by weight), pelleted intoPHA (62% by weight). Others are known to those of ordinary skill in thefield of polymer processing.

If desired, an optional nucleating agent is added to the compositions ofthe invention to aid in its crystallization if needed. Nucleating agentsfor various polymers are simple substances, metal compounds includingcomposite oxides, for example, carbon black, calcium carbonate,synthesized silicic acid and salts, silica, zinc white, clay, kaolin,basic magnesium carbonate, mica, talc, quartz powder, diatomite,dolomite powder, titanium oxide, zinc oxide, antimony oxide, bariumsulfate, calcium sulfate, alumina, calcium silicate, metal salts oforganophosphates, and boron nitride, cyanuric acid and the like.

It has been found that a combination of PLASTISTAB® 2442 (4 phr),PARAPLEX® G-62 (4.5 phr) and the plasticizer diisononyl adipate (18 phr)additives in a PVC/PHA, PMMA/PHA or POM/PHA blend formulations describedhere give very good light stabilizing properties so that no UV lightstabilizers are needed for outdoors uses of the formulation.

Application of the Compositions

PVC, PMMA or POM and the compositions described herein may be used formany applications, including but not limited to construction materials(e.g., doors, windows, siding, pipes, tubing, coatings), packagingmaterial, automotive products and also medical applications (e.g. tubingor bags for liquid storage).

For the fabrication of useful articles, the compositions describedherein are processed preferably at a temperature above the crystallinemelting point of the polymers but below the decomposition point of anyof the ingredients (e.g., the additives described above, with theexception of some branching agents) of the polymeric composition. Whilein heat plasticized condition, the polymeric composition is processedinto a desired shape, and subsequently cooled to set the shape andinduce crystallization. Such shapes can include, but are not limited to,a fiber, filament, film, sheet, rod, tube, bottle, or other shape. Suchprocessing is performed using any art-known technique, such as, but notlimited to, extrusion, injection molding, compression molding, blowingor blow molding (e.g., blown film, blowing of foam), calendaring,rotational molding, casting (e.g., cast sheet, cast film), orthermoforming. Thermoforming is a process that uses films or sheets ofthermoplastic. The polymeric composition is processed into a film orsheet. The sheet of polymer is then placed in an oven and heated. Whensoft enough to be formed it is transferred to a mold and formed into ashape.

During thermoforming, when the softening point of a semi-crystallinepolymer is reached, the polymer sheet begins to sag. The window betweensoftening and droop is usually narrow. It can therefore be difficult tomove the softened polymer sheet to the mold quickly enough. Measuringthe sag of a sample piece of polymer when it is heated is therefore away to measure the relative size of this processing window forthermoforming.

Films, Sheets and Tapes

The compositions of the inventions are for producing films, sheets andtape with certain properties and/or characteristics.

The films or sheets can be single layer or multilayer. Suitablethicknesses include, 0.005 mm to about 0.01 mm, 0.01 mm, 0.02 mm, 0.03mm, 0.04 mm, 0.05 mm, 0.06 mm, 0.07 mm, 0.08 mm, 0.09 mm or 0.1 mm. Thefilm or sheet can be optically clear or opaque. The films and sheets canbe further processed to tapes. The tapes can optionally include anadhesive layer on one or both sides. Also included are laminates.

Applications

The compositions described herein can be processed into films of varyingthickness, for example, films of uniform thickness ranging from 1-200microns, for example, 10-75 microns, 75 to 150 microns, or from 50-100microns. Film layers can additionally be stacked to form multilayerfilms of the same or varying thicknesses or compositions of the same orvarying compositions.

Blow molding, which is similar to thermoforming and is used to producedeep draw products such as bottles and similar products with deepinteriors, also benefits from the increased elasticity and melt strengthand reduced sag of the polymer compositions described herein.

Articles made from the compositions can be annealed according to any ofthe methods disclosed in International Publication No. WO 2010/008445,which was published in English on Jan. 21, 2010, and designated theUnited States, and is titled “Branched PHA Compositions, Methods ForTheir Production, And Use In Applications,” which was filed in Englishand designated the United States. This application is incorporated byreference herein in their entirety.

The compositions described herein are provided in any suitable formconvenient for an intended application. For example, the composition isprovided in pellet for subsequent production of films, coatings,moldings or other articles, or the films, coatings, moldings and otherarticles.

The polymeric compositions of the present invention can be used tocreate, without limitation, a wide variety of useful products, e.g.,automotive, consumer durable, consumer disposable, construction,electrical, medical, and packaging products. For instance, the polymericcompositions can be used to make, without limitation, films (e.g.,packaging films, agricultural film, mulch film, erosion control, haybale wrap, slit film, food wrap, pallet wrap, protective automobile andappliance wrap, etc.), bags (e.g., trash bags, grocery bags, food bags,compost bags, etc.), hygiene articles (e.g., diapers, feminine hygieneproducts, incontinence products, disposable wipes, etc.), coatings forpelleted products (e.g., pelleted fertilizer, herbicides, pesticides,seeds, etc.), packaging (including, but not limited to, packaging andcontainers for food and beverage products, cosmetic products, detergentsand cleaning products, personal care products, pharmaceutical andwellness products), golf tees, caps and closures, agricultural supportsand stakes, paper and board coatings (e.g., for cups, plates, boxes,etc.), thermoformed products (e.g., trays, containers, yoghurt pots,plant pots, noodle bowls, moldings, etc.), housings (e.g., forelectronics items, e.g., cell phones, PDA cases, music player cases,computer cases, printers, calculators, LCD projectors, connectors, chiptrays, circuit breakers, plugs, and the like), wire and cable products(including, but not limited to, wire, cable and coatings for wire andcable for vehicles, cars, trucks, airplanes, aerospace, construction,military, telecommunication, utility power, alternative energy, andelectronics), industrial products (such as, but not limited to,containers, bottles, drums, materials handling, gears, bearings, gasketsand seals, valves, wind turbines, and safety equipment), products fortransportation (such as, but not limited to, automotive aftermarketparts, bumpers, window seals, instrument panels, consoles, under hoodelectrical parts, and engine covers), appliances and appliance parts(such as, but not limited to, refrigerators, freezers, washers, dryers,toasters, blenders, vacuum cleaners, coffee makers, and mixers),articles for use in building and construction (such as, but not limitedto, fences, decks and rails, floors, floor covering, pipes and fittings,siding, trim, windows, doors, molding, and wall coverings), consumergoods and parts for consumer goods (such as, but not limited to, powerhand tools, rakes, shovels, lawn mowers, shoes, boots, golf clubs,fishing poles, and watercraft), healthcare equipment (including, but notlimited to, wheelchairs, beds, testing equipment, analyzers, labware,ostomy, IV sets, wound care, drug delivery, inhalers, and packaging). Inshort, the polymeric products described herein can be used to make theitems currently made from conventional petroleum-based polymers.

In general, there is an increasing consumer demand for products thathave increased biobased content. Where the PHA's of the currentinvention are made from renewable resources then the exact percentage ofrenewable carbon can be determined via ASTM D6866—an industrialapplication of radiocarbon dating. ASTM D6866 measures the “modern”Carbon 14 content of biobased materials; and since fossil-basedmaterials no longer have Carbon 14, ASTM D6866 can effectively dispelinaccurate claims of biobased content. Accuracy of radioanalyticalprocedures used to determine the biobased content of manufacturedproducts is outlined in Norton et al., Bioresource Technology,98:1052-1056 (2007), incorporated herein by reference.

In the compositions of the invention for making articles the bio-basedchemicals comprise at least about 50% (e.g., at least about 60%, atleast about 65%, at least about 70%, at least about 75%, at least about80%, at least about 85%, at least about 90%, or at least about 95%, atleast about 96%, at least about 97%, at least about 98%, at least about99%, up to 100%) bio-based content based on the total weight of thecomposition. In this regard, the synthetic polymer is composed of asufficient amount of bio-based components (i.e., the precursors aresubstantially composed of materials derived from renewable resources),and the composition comprises a sufficient amount to achieve the desiredbio-based content level.

The specific examples below are to be construed as merely illustrative,and not limitative of the remainder of the disclosure in any waywhatsoever. Without further elaboration, it is believed that one skilledin the art can, based on the description herein, utilize the presentinvention to its fullest extent. All publications cited herein arehereby incorporated by reference in their entirety.

EXAMPLES Experimental Methods Measurement of the Mechanical Properties

Tensile properties of the PVC/PHA blends were measured according to ASTMD638-03; flexural properties were measured according to ASTM D790-03;notched Izod Impact properties were measured according to ASTM D256-06;Elmendorf resistance to tear propagation was measured according to ASTMD 1922-06; Shore D Hardness was measured according to ASTM D2240 and lowtemperature brittleness was measured according to ASTM D746 (the resultsare reported as pass or fail (break on impact)).

Measurement of Melt Strength and Viscosity

Melt strength, G′, and viscosity, η*, was measured using oscillatorytorsional rheology. The measurements were performed using a TAInstruments AR2000 rheometer employing strain amplitude of 1%. First,pellets (or powder) were molded into 25 mm diameter discs that wereabout 1200 microns in thickness. The disc specimens were molded in acompression molder set at about 165-177° C., with the molding time ofabout 30 seconds. These molded discs were then placed in between the 25mm parallel plates of the AR2000 rheometer, equilibrated at 185° C., andsubsequently cooled to 160° C. for the frequency sweep test. A gap of800-900 microns was used, depending on the normal forces exerted by thepolymer. The melt density of PHB was determined to be about 1.10 g/cm³at 160° C.; this value was used in all the calculations.

Specifically, the specimen disc was placed between the platens of theparallel plate rheometer set at 185° C. After the final gap wasattained, excess material from the sides of the platens was scraped. Thespecimen was then cooled to 160° C. where the frequency scan (from 625rad/s to 0.10 rad/s) was then performed; frequencies lower than 0.1rad/s were avoided because of considerable degradation over the longtime it takes for these lower frequency measurements. The specimenloading, gap adjustment and excess trimming, all carried out with theplatens set at 185° C., takes about 2½ minutes. This was controlled towithin ±10 seconds to minimize variability and sample degradation.Cooling from 180° C. to 160° C. (test temperature) was accomplished inabout four minutes. Exposure to 180° C. ensures a completely moltenpolymer, while testing at 160° C. ensures minimal degradation duringmeasurement.

During the frequency sweep performed at 160° C., the following data wascollected as a function of measurement frequency: η* or complexviscosity, G′ or elastic modulus (elastic or solid-like contribution tothe viscosity) and G″ or loss modulus (viscous or liquid-likecontribution to the viscosity). For purposes of simplicity, G′ measuredat an imposed frequency of 0.25 rad/s as a measure of “melt strength”was used. Higher G′ value therefore translated to higher melt strength.

Measurement of Glass Transition Temperature (T_(g)) and PercentCrystallinity

The glass transition temperature, T_(g), of PVC, PMMA or POM/PHA blendswas measured using a TA Instruments Q100 Differential ScanningCalorimeter (DSC). The unknown PHA samples were put through aheating-cooling-heating cycle at 10° C./min from −50° C. to 200° C. TheTg was then measured using the second heating curve by taking themidpoint of the change in slope of the glass transition. Percentcrystallinity was also measured using the TA Instruments Q100 DSC. Theheat of melting (J/g) for each unknown PHA sample was measured byintegrating the area under the respective melting peak. The heat ofmelting for each unknown PHA sample was then divided by the heat ofmelting from a PHA sample of known % crystallinity and multiplied by its% crystallinity value.

Measurement of Thermal Stability

The thermal stability of PVC/PHA blends was measured using a TAInstrument Q500 TGA (Thermal Gravimetric Analyzer). Approximately 40-50mg of the blend was placed in to a tared platinum pan and loaded, withthe aid of an autosampler, on to the instrument balance and then TGAfurnace raised around the sample. The sample was then heated undernitrogen gas, at rates of 2.5 to 20° C./min from room temperature to600° C. The weight loss of the sample versus the temperature wasrecorded and plotted. The slopes of the weight loss versus temperaturewere calculated and the activation energies (E_(a)) for thermaldegradation were determined using the Kissinger equation which is asfollows:βE _(a) /RT ² _(m) =A(n(1−α)^(n−1) _(m))exp(−E _(a) /RT _(m)),where

-   α—conversion;-   E_(a)—apparent activation energy (kJ/mol)-   A—pre-exponential factor-   β—heating rate (° C./min)-   R—general gas constant (J/mol ° K)-   T_(m)—temperature at maximum degradation rate (° K)-   n—reaction order

The Kissinger method has shown that the product n(1−α)^(n−1) _(m) equals1 and is independent of the heating rate. The dependence of ln(β/T²_(m)) vs. 1/RT_(m) represents a straight line whose slope can be used tocalculate E_(a) and intercept be used to calculate the pre-exponentialfactor.

Measurement of PHA Molecular Weight

The absolute weight average molecular weight for the PHA materials wasdetermined by using a flow injection polymer analysis system (TDAmax™,Viscotek Corp). It is a liquid chromatography technique whereby thepolymer to be measured is first dissolved in a solvent, filtered andthen injected into the FIPA instrument. Once injected, the polymersolution is carried by mobile phase solvent and elutes through a single,low volume size exclusion chromatography column. The column acts toseparate the polymer, solvent and any other impurities present in thesample. The detection system consists of a refractive index, lightscattering and solution viscosity detectors. The absolute weight averagemolecular weight of the polymer is determined using the light scatteringdetector.

To prepare the polymer sample, it was first dissolved in chloroform to aconcentration of 2.0 mg/ml at 60° C. After cooling the sample, it wasthen filtered with a 0.2 micrometer Teflon syringe filter and injectedinto the instrument. The FIPA unit operated at a temperature of 45° C.with tetrahydrofuran solvent as the mobile phase. The mobile flow ratewas 1.0 ml/min. A 100 μl injection volume was used for the analysis ofthe polymer solution. Once the sample chromatogram was collected, it wasthe analyzed with the Viscotek Omni-Sec software to determine theabsolute weight average molecular weight in units of grams/mole.

Measurement of PHA Composition

The weight percent 4-hydroxybutyrate contained in the PHA copolymers wasdetermined by acid alcoholysis followed by GC-FID analysis. A 10-15 mgsample of the dry copolymer was first weighed in to a test tube. Then2-5 ml of a reagent containing n-butanol (99%, EMD), 4M HCl in dioxane(Sigma Aldrich) and the intenral standard diphenylmethane was pipettedin to the test tube. The test tube was capped and heated at 93° C. for 6hours using a heater block. After the alcoholysis reaction wascompleted, the test tube contents were cooled to room temperature and2-5 ml of DI water was added. The mixture was centrifuged and theorganic top layer was pipetted out of the test tube and into a GC vial.The GC vial contents were then run on an Agilent Technologies, Model6890N, GC-FID System having a ZB-35 30 m×0.25 mm×0.25 μm GC-FID column(Phenomenex). Standards for quantitating the weight % 4HB in thecopolymer were also prepared using γ-butyrolactone (99%, Sigma Aldrich).

Biobased Content

The biobased content or percent ¹⁴C carbon relative to the total carbonin the PHA samples was measured by the radiocarbon dating methodaccording to ASTM D6866.

PHA Materials

The PHA polymers utilized in the blend examples along with their weightaverage molecular weights, compositions, glass transition temperature(Tg), % crystallinity and biobased content are summarized in Table 1.All of the PHA's utilized in the PVC, PMMA or POM/PHA blends werecopolymers of 3-hydroxybutyrate and 4-hydroxybutyrate or where indicatedwere blends of these copolymers having different % 4HB content. PHA Fwas a thermolyzed version of PHA E in order to lower the molecularweight of the PHA resin. Table 1 also shows the weight percent rubberfor each PHA blend or individual copolymer. When the % 4HB in a P3HB-4HBcopolymer is above 25% by weight, the properties of the PHA are morelike that of an amorphous rubber material. When these are blended withP3HB homopolymers, a multiphase material can be created which has asignificant rubber or amorphous phase. The weight % rubber in Table 1refers to the weight percent of the rubbery P3HB-4HB copolymer presenthaving a weight % 4HB of greater than 25%.

TABLE 1 Summary of PHA polymers used in the PVC, PMMA and POM/PHA blendexamples. All of the PHA's were either copolymers of 3-hydroxybutyrateand 4-hydroxybutyrate or where indicated blends of these withpoly-3-hydroxybutyrate. Total Weight % Weight % Crys- % Bio- % Rubber Tgtal- based Polymer ID M_(w) 4HB PHA (° C.) linity Content PHA A* —4.4-5  0  1.3 ± 1 43-45 94 PHA B** — 8-9 0  −4 ± 1 38-43 90 PHA C***492,000 12-15 40 −12 ± 2 26-28 84 PHA D — 11 0  −7 24-26 — PHA E⁺1,538,000  29.6 100 −14 0-1 66 PHA F⁺ 900,000 29.6 100 −14 0-1 66 PHAG**** — 16-18 40 −12 ± 2 26-28 — PHA H^(†) 400,000 to 55 100 −25 ± 1 0-1100  500,000 *PHA A: Blend of 55-65% P3HB and 35-45% P3HB-4HB copolymerwith 8-14% 4HB by weight. **PHA B: Blend of 18-22% P3HB, 77-83% P3HB-4HBcopolymer with 8-14% 4HB by weight. ***PHA C: Blend of 34-38% P3HB,22-26% P3HB-4HB copolymer with 8-14% 4HB by weight and 38-42% P3HB-4HBcopolymer with 25-33% 4HB by weight. ****PHA G: Blends of 10-14% P3HB,46-50% P3HB-4HB copolymer with 8-14% 4HB by weight and 38-42% P3HB-4HBcopolymer with 25-33% 4HB by weight. ⁺Tianjin SOGREEN ™ P3HB-4HBcopolymer with 30% by weight 4HB. ^(†)PHA H: Copolymer of P3HB-4HB with55% 4HB content made from glucose feedstock. See PCT Application No.PCT/US2013/028913 incorporated herein by reference. 5-10% by weightCaCO₃ was also added to the PHA to facilitate handling of the rubbermaterial.PVC/PHA Formulations and Preparation

Polyvinylchloride (PVC) resins with K-values of 57 and 70 (OXY 185F, 190and 240 from OxyVinyls LP or G2100 from S&E Specialty Polymers) wereblended with the PHA's listed in Table 1. PVC formulations are usuallyclassified by their durometer hardness values as rigid, semi-rigid orflexible (see ASTM classifications). In the following examples, the PVCformulations cover a range of compounds varying from rigid (0%plasticizer) to semi-rigid (18 phr plasticizer), to flexible (36 phrplasticizer). Diisodecyl phthalate (DIDP, Sigma Aldrich) was used as themonomeric, “nonextractable” plasticizer in the base PVC resinformulations. Heat stabilizers were also used in the PVC/PHAformulations including BaZn carboxylates such as MARK™ 4781A (Chemtura)or PLASTISTAB™ 2442 (AM Stabilizers Corp.) for preparing transparentPVC/PHA blends. A solid polymeric stabilizer NAFTOSAFE™ PKP1028 (ChemsonGesellschaft fur Polymer-Additive mbH) for preparing opaque PVC/PHAformulations added @2.5 phr. Two secondary heat stabilizers were alsoadded to the PVC/PHA formulations. They were PLASTISOY™ 7.0 (CHS Inc.Corp.), epoxidized soybean oil, added @4.5 phr and HIPURE™ 4 (DoverChemical Corp.), tris(nonylphenyl)phosphite, added @0.5 phr. The changein PVC impact properties by adding PHA was benchmarked against thecommercial impact modifiers KANE ACE™ B-22(methylmethacrylate/butadiene/styrene (MBS) copolymer, Kaneka) and ABSBLENDEX™ 3160 (an acrylonitrile/butadiene/styrene copolymer, GalataChemicals). The acrylic processing aid KANE ACE™ PA-20 (Kaneka) was usedfor benchmarking against PHA as a melt fluxing additive. The peroxidebranching agent TRIGONOX® 101 (Akzo Nobel) was used to modify the PHA'sprior to mixing the PHA with PVC. The peroxide was melt blended andreacted with the PHA's using a Prism 16 mm twin screw extruder. Afterreacting, the melt mixture was extruded into a strand and cooled in awater bath at room temperature. After cooling the strands were eitherhand cut or cryogenically ground. TRIGONOX® 117 (Akzo Nobel) peroxideand pentaerythritol triacrylate (Sartomer) co-agent were used to preparea masterbatch PVC impact modifier formulation with PHA C,acrylonitrile-styrene-acrylate (ASA) PVC impact modifier (GalataChemicals) and chlorinated polyethylene (CPE) PVC impact modifier (DowChemicals).

The PVC/PHA formulations were prepared using a two roll mill for thecompounding. The temperature for the rollers was set to 330° F. PHA'slisted in Table 1 were added to the PVC resin @5 to 28 phr loading. Allof the PVC/PHA blends released nicely from the rolls and it was possibleto produce transparent blends when appropriate PVC heat stabilizers wereused.

The milled PVC/PHA compounded sheets produced were then compressionmolded at 165-175° F. into the samples for tensile, tear strength, IzodImpact and other tests.

PMMA/PHA Formulations and Preparation

Polymethylmethacrylate (PMMA) resin from Evonik (PLEXIGLAS™ 8N) wasblended with the polyhydroxyalkanoates PHA C and G (see Table 1). Table2 below summarizes the properties of the PMMA resin:

TABLE 2 PMMA grades and properties. Property PLEXIGLAS ™ 8N Tg (° C.)117 MFI (g/10 min, 230° C., 3.8 kg) 3.57 Density (g/cm³) 1.19 Tensilestress at break (MPa) 77 Elongation at break (MPa) 5.5 Tensile modulus(GPa) 3.3 Charpy unnotched impact (J/cm²) 2 Vicat softening point (° C.)108 Haze (%) ≦0.5 Transmission, visible (%) 92 Refractive index 1.49

The PMMA/PHA blends were prepared using a Prism twin screw, 16 mm,extruder having nine heated zones. The following temperature profile(inlet to outlet die) was used to process the blends 190° C./190°C./185° C./185° C./185° C./180° C./180° C./180° C./175° C./175° C. Aftermelt extrusion, the blend was pelletized, the pellets were dried in anoven at 50° C. overnight and the dried pellets were compression moldedat 185° C. into samples for measuring the thermal and mechanicalproperties.

POM/PHA Formulations and Preparation

Polyoxymethylene (POM) resins (copolymers of methylene oxide andethylene glycol) were obtained from Korean Plastic Engineering and wereblended with the polyhydroxyalkanoates PHA C and G (see Table 1). ThePOM resins were KEPITAL™ F20-30—an injection molding grade and KEPITAL™F30-30—a low viscosity injection molding grade. For comparison an impactmodified POM grade having 5% TPU, KEPITAL™ TE-21, was also tested.

The POM/PHA blends were prepared using a Prism twin screw, 16 mm,extruder having nine heated zones. The following temperature profile(inlet to outlet die) was used to process the blends 190° C./190°C./185° C./185° C./180° C./180° C./180° C./175° C./175° C./175° C. Aftermelt extrusion, the blend was pelletized, the pellets were dried in anoven at 50° C. overnight and the dried pellets were compression moldedat 185° C. into samples for measuring the thermal and mechanicalproperties.

Example 1 Addition of a Rubbery PHA Copolymer to Rigid PVC—Effect onThermal, Mechanical and Melt Properties

In this example, PHA E, a rubbery 30% 4HB copolymer, was added to arigid PVC formulation (0% DIDP plasticizer) @28 phr (20% by weight) andthe effect on the impact properties of the blend were evaluated. Table 3summarizes the thermal and mechanical testing results for this blend.

TABLE 3 Summary of mechanical and thermal properties of a rigid PVC@100phr (0% DIDP)/PHA E @28 phr blend. Property Formulation 1 Tg (° C.) 32.3Tensile Modulus (MPa) 1407 Tensile Strain @break 102 (MPa) TensileToughness 3.31 (J) Flexural Modulus (MPa) 1202 Low Temperature passedBrittleness (5° C.) Izod Impact Strength (ft >18 lb/in) Shore D Hardness66

The results in Table 3 show that the rubbery PHA E was completelymiscible with the PVC as evidenced by the single T_(g) value measured byDMA analysis. Since pure PVC has a single T_(g) at approximately 70° C.,the results in Table 1 also indicated that the rubbery PHA E was veryeffective at plasticizing the rigid PVC. According to the measured T_(g)value, the PVC blend T_(g) was reduced by a factor of 2. The mechanicaltesting results showed that the rubbery PHA E added @28 phrsignificantly improved the impact strength and tensile toughness of thePVC without compromising the tensile or flexural moduli. The Hardnessvalue also did not appear to change significantly with the addition ofthe PHA E. In comparison, PVC compounded with the commercial impactmodifier KANE ACE™ B-22 only showed an impact strength of 1.9 ft lb/in.The PHA E therefore acted as a PVC plasticizer, impact modifier andprocessing aid all in one. This would eliminate the need to havemultiple additives performing different functions for formulating PVCproducts thereby reducing costs.

The complete miscibility of the PHA E in PVC could be explained bycomparing the solubility parameters of the PHA E copolymer componentswith that of PVC resin. The solubility parameter, δ, is a numericalestimate of the degree of interaction between materials and can be agood indication of solubility, particularly for non polar materials suchas polymers. Materials with similar δ values are likely to be miscible.Table 4 shows the calculated solubility parameters (total, polar andnonpolar (dispersion) components see M. Terada, R. H. Marchessault,International Journal of Biological Macromolecules, 25, 1999, p 207-215)for PVC, poly-3-hydroxybutyrate (P3HB), poly-4-hydroxybutyrate (P4HB),diisodecylphthalate (DIDP) and poly-methyl-methacrylate (PMMA). Thelatter two compounds are very common plasticizers and impact modifiersused in PVC formulations. As can be seen in Table 4, the calculatedsolubility parameters (using the Van Krevelen method) for PVC were mostsimilar to P3HB polymer. This could explain why the PHA E which is 70%3HB was found to be miscible with the PVC. It could be assumed thatsimilarly to PVC/PMMA blends, the miscibility of PVC/PHA was attributedto the exothermic mixing arising from the formation of weak hydrogenbonds between the carbonyl groups of the PHA and the methine protons ofthe PVC. The best PVC impact and processing modifiers on the markettoday are based on acrylate copolymers such as P(MMA-co-BA) orP(MMA/co-MA) listed in Table 4. The PVC/PMMA blend is known to bemiscible, while the impact absorbing PMA or PBA form immiscible blendswith PVC. The non-toughening PMMA component is used to anchor themodifier to the PVC chains, while the phase separated PMA or PBAcomponent provides the toughening. By the analogy with MMA and MAsolubility parameters, it could be expected that P(3HB-co-4HB) with30-45% 4HB would provide similar if not better modification than acrylicimpact modifiers.

TABLE 4 Calculated solubility parameter values, δ, for PVC, PHA andother additives. Parameters calculated using the monomer groupcontribution method of Van Krevelen (Properties of Polymer, 4^(th) Ed.,Elsevier, 2009). Included in the calculations are the polar and nonpolarcontributions to the total solubility parameter. Polymer δ_(total)(J/cm³)^(1/2) δ_(polar) (J/cm³)^(1/2) δ_(nonpolar) (J/cm³)^(1/2) PVC21.2 24.1 16.1 P3HB 20.4 27.3 17.1 P4HB 19.8 27.3 16.1 PMMA 19.5 27.316.7 PMA 20.4 27.3 17.1 DIDP 17.6 27.3 16.3

FIGS. 1 and 2 show the melt behavior of the PVC/PHA E 28 phr blend(sample #20) as compared to a PVC/DIDP 18 phr formulation (sample #21)and PVC/KANE ACE™ B22 formulation (sample #18). The data in FIGS. 1 and2 was collected using rotational rheometry under standard conditions(preheating at 180° C., testing at 160° C.).

The data in FIGS. 1 and 2 shows that the PVC formulations with the PHA Eadditive, as compared to PVC with DIDP plasticizer or DIDP plasticizerand KANE™ ACE B22 impact modifier, had both higher viscosity and elasticmodulus at all shear rates tested. This would be beneficial for instancein PVC blow molding or film applications requiring higher melt strength.

Example 2 Addition of PHA to Rigid PVC—Effect of Thermal StabilizerPackage

In this example, changes in the impact strength for a rigid PVC/PHAblend versus the type of PVC thermal stabilizer incorporated arecompared. The PVC resin used to prepare the samples was OXYVINYLS™ 240 ahigh molecular PVC with K=70. The PHA used was the amorphous or rubberycopolymer, PHA F, having a % 4HB content of 30% by weight. The samplesfor impact strength testing (Formulations #20 and #32) were preparedaccording to the procedure described previously. Formulation #20 shownin Table 5 was prepared using the liquid BaZn stabilizer, M4781A (GalataChemicals), having a Ba/Zn ratio=5.7 and a 5.33% by wt. phosphoruscontaining compound while Formulation 32 was stabilized with a solidBaZn salt of unknown composition (NAFTOSAFE™ PKP1028, Chemson PolymerAdditive AG) and a phosphite (Doverphos-HIPURE™ 4, ICC Industries). Bothformulations contained the same amount of epoxdized soybean oil(secondary plasticizer/heat stabilizer PLASTISOY™ 7, CHS Inc.) and had aShore hardness value of about 66D. The data in Table 5 shows thatFormulation #32 made with the solid BaZn salt stabilizer had an impactstrength an order of magnitude lower than that measured for Formulation#20 which had the liquid BaZn stabilizer added. The lower impactstrength of Formulation #32 could have been due to lost elasticity ofthe modifier, if it went through significant degradation duringprocessing or due to dispersion problems. TGA data showed that theactivation energy of thermal degradation was significantly lower forFormulation #32 indicating that this sample had lower thermal stability.

TABLE 5 Summary of rigid PVC/PHA F Formulations #20 and #32 preparedwith different PVC stabilizers. Formulation Formulation 20 32 PVC, K =70 100 100 BaZn solid stabilizer 2.5 Epoxidized Soybean Oil 4.5 4.5Phosphite (HiPure 4) 0.5 BaZn liquid stabilizer 4 PHA F 28 28Thermal/Mechanical Properties Tg (° C.) DMA 32.3 36.68 tan δ, max, (°C.) DMA 70.34 72.69 Flex modulus, (MPa) 1202 1214 Notched Izod Impact(ft lb/inch) >18 1.7

The above experiment was repeated by adding 18 phr DIDP plasticizer toboth #20 and #32 Formulations. The results showed that Formulation #20again had much higher impact strength as compared to #32 likely due tobetter thermal stabilization.

Example 3 Addition of Crosslinked PHA to Rigid PVC

In this example, PHA C (40% amorphous rubber P3HB-4HB with 28-32% by wt.4HB) and H (100% amorphous rubber P3HB-4HB with 55% by wt. 4HB) werecrosslinked prior to melt blending with a rigid PVC polymer in order toenhance the impact modification properties of the PVC. Initially, PHA Cand H were compounded with a peroxide initiator masterbatch consistingof 5% by weight T101™ peroxide blend with PHA B. For the compounding ofPHA C or H with the peroxide masterbatch, a Prism, 16 mm twin screwextruder operating @150 rpm was used with the following extrusiontemperatures (inlet to outlet): 172° C./174° C./175° C./177° C./177°C./179° C./179° C./179° C. Following reactive extrusion, the crosslinkedPHA C or H was formed into strands and cooled in a water bath set atroom temperature. The strands were then dried and cut into pellets orcryogrind under liquid nitrogen into a powder. The final concentrationof peroxide in PHA C and H was varied from 0.05 to 0.2% by weight PHA byadding different weights of the peroxide masterbatch. Torsionalrheometry was carried out on the compounded PHA's to verify thatcrosslinking had occurred. PHA C or H was then dry blended with K70 PVC(GG2100) using a two-roll mill @165° C. Samples of the PVC/PHA blendwere then compression molded and mechanically tested. Table 6 shows asummary of the PVC/PHA formulations tested and their results.

TABLE 6 Summary of mechanical testing data for rigid PVC/crosslinked PHAblends. Formulation 33 34 35 36 37 PVC K70 (G2100) 100 100 100 100 100PHA H (0.15% T101) 15 PLASTISTAB ™ 2442 4 4 4 4 4 BaZn thermalstabilizer PHA H (0.2% T101) 15 PHA H (0.1% T101) 15 PHA C (0.2% T101)15 PHA H (0.05% T101) - 15 cryoground Mechanical Properties Notched IzodImpact, 1.05 1.40 2.13 2.25 1.62 ft lb/inch Flexural Modulus, MPa 27802421 2439 2256 2642 Flexural Stress @5%, 94.4 88.5 93.8 90.5 95.1 MPaTensile toughness, J 1.04 0.90 0.75 0.99 0.79 Tensile modulus, MPa 23202265 2350 2242 2145

The results in Table 6 show that crosslinking the PHA's with peroxidesignificantly improved the toughness and impact resistance of the rigidPVC. The highest impact modification was found for the PVC/PHA H blend(% 4HB content 55%) where the level of peroxide in the PHA H was at 0.2%by weight PHA. The Notched Izod impact strength can be seen to increasewith increasing peroxide concentration in the PVC/PHA H blends. Howevera decrease in the flexural modulus was observed as the concentration ofperoxide increased. A similar trend was observed for the tensile moduluswith increasing peroxide concentration. While the addition of peroxideto the PHA C or H was shown to improve the impact properties of therigid PVC, the concentration would to be optimized depending on themechanical properties required for a given application.

Example 4 Preparation of PHA Impact Modifier Masterbatch for Rigid PVC

This example outlines a procedure for preparing a PHA impact modifiermasterbatch formulation for adding to rigid PVC. The PHA masterbatch wascomposed of PHA C melt blended with 0.1% by weight TRIGONOX® 117 and0.1% weight pentaerythritol triacrylate to induce crosslinking/branchingof the PHA C polymer (40% rubber P3HB-4HB copolymer with 28-32% 4HB).The crosslinked PHA C polymer was then melt blended in a 2/1 ratio(PHA/polymer) with either ASA (acrylonitrile-stryene-acrylate, GalataChemicals) or CPE (chlorinated polyethylene, Dow) polymer. Afterpreparation of the masterbatch, it was dry blended with rigid PVC (K=70)and compounded on a two roll mill at 165° C. for about 5 minutes. Testbars were then compression molded from the PVC formulations and testedaccording to ASTM D790-03 for flexural and ASTM D256-06 for notched Izodimpact properties.

TABLE 7 Formulation summary of PHA impact modification masterbatches andrigid PVC. Components are in parts per hundred (phr). ComponentFormulation #1 Formulation #2 PVC (K = 70) 84.8 84.8 PHA C 10 10 ASA 5 —CPE — 5 TRIGONOX ® 117 0.1 0.1 Pentaerythritol 0.1 0.1 triacrylate

The notched Izod impact and flex modulus results showed that the PVCFormulation #1 having the ASA/crosslinked PHA C masterbatch impactmodifier showed a 4-9 times improvement in notched Izod impact ascompared to PVC having only ASA impact modifier present while the flexmodulus showed a 9% decrease for the ASA/crosslinked PHA C modifier. PVCFormulation #2 with CPE/crosslinked PHA masterbatch showed a 3 timesimprovement in notch Izod impact properties with a 7% improvement inflex modulus as compared to PVC having only the CPE impact modifierpresent. The results showed that blending of crosslinked PHA to ASA andCPE commercially available PVC impact modifiers provided synergisticimprovements in rigid PVC performance to levels that are nearlyequivalent to ABS (acrylate-butadiene-styrene) and MBS(methacrylate-butadiene-styrene) impact modifiers.

Example 5 Addition of a Rubbery PHA to Semi-Rigid PVC—Effect on Thermaland Mechanical Properties

In this example, a semi-rigid PVC base resin was first prepared byadding 18 phr DIDP plasticizer. To this base PVC resin, other additiveswere then mixed in order to evaluate their effect on the thermal andmechanical properties of the semi-rigid PVC blend (formulations #2-8).The PVC additives that were evaluated and compared included PHA D (norubber PHA present), PHA E (100% rubber PHA) and PHA F (a lowermolecular weight version of PHA E) and the KANE™ ACE B22 impactmodifier. As a comparison, the semi-rigid PVC base resin without anyadditives was also included in the analysis.

Table 8 summarizes the thermal and mechanical data collected for thesemi-rigid PVC formulations. Also included are qualitative observationson the optical clarity of the formulations. The results in Table 8showed that at the 5 phr loading level, the rubber PHA E impartedsimilar impact strength performance to the semi-rigid PVC resin ascompared to the commercial impact modifier KANE ACE™ B22. However at the18 phr loading level, rubber PHA F gave 6 times the impact strength ascompared to the 10 phr KANE ACE™ B22 semi-rigid PVC sample. The lowermolecular weight of the PHA F likely also contributed to the enhancedimpact strength performance. Improved low temperature impact brittlenessperformance as well as plasticization effect was also observed for therubber PHA E and F additives as compared to the KANE ACE™ B22 additive.The PHA D (high molecular weight 11%-4HB copolymer) on the other handdid not impart any improvement to the impact strength (at 5° C. and roomtemperature) which indicated that this copolymer would not be a goodchoice as an impact modifier for the semi-rigid PVC. This copolymerhowever still provided significant plasticization as shown by the lowerTg value. Qualitatively it was additionally observed that the PHAadditives gave much clearer blends with the semi-rigid PVC base resinwhen the loading of PHA was 1 to 15 phr.

TABLE 8 Summary of thermal and mechanical properties of semi-rigid PVC@100 phr/PHA additive blends. The semi-rigid PVC resin was compoundedwith 18 phr DIDP plasticizer. Formu- Formu- Formu- Formu- Formu- Formu-Formu- lation 2 lation 3 lation 4 lation 5 lation 6 lation 7 lation 8Semi-rigid PVC + 107.5 phr 107.5 phr 107.5 phr 107.5 phr 107.5 phr 107.5phr 107.5 phr 18 phr DIDP KANE ACE ™ B22   5 phr   10 phr PHA D   10 phrPHA E   5 phr   10 phr PHA F   18 phr T_(g) (° C.) 35.3 41.2 46 29.225.6 23.1 30 Tensile Modulus (MPa) 1298 1316 1451 740 469 184 756Tensile Strain @Break 152 144 130 174 168 188 168 (MPa) TensileToughness (J) 4.60 3.86 3.47 4.42 4.08 3.70 5.57 Flexural Modulus (MPa)952 1057 865 — — 149 430 Low Temperature failed failed failed passedpassed passed Failed Brittleness (5° C.) Izod Impact Strength 1.25 0.951.93 0.94 — 7.42 0.90 (ft lb/in) Shore D Hardness 58 67 62 — — 50 56Optical Clarity clear opaque opaque clear clear opaque clear

The thermal stability of Formulations 2 and 6 in Table 8 were comparedusing TGA to measure the activation energies for thermal degradation. Athird sample was also included for comparison which was composed of PVCwith 28 phr of the PHA E and no DIDP plasticizer.

FIG. 3 shows the TGA curve and its derivative curve for the PVC+ 18 phrDIDP (Formulation 2) polymer. Two distinct weight loss events,corresponding to onset of thermal degradation, were observed: the firststarted at about 280° C. with a peak decomposition temperature at about304° C. while the second event started at about 450° C. These weightloss events are typical for PVC polymers and correspond to the thermalbreakdown of the PVC with a first weight loss generating hydrochloricacid and leaving behind conjugated double bonds while the second weightloss involves the formation and volatilization of cyclic species due tothe intramolecular cyclization of the conjugated sequences. FIG. 4 showsan overlay plot of the TGA curves for Formulations 2 and 6 as well asthe PVC+28 phr rubber PHA blend. The plot shows that while the onset forthermal degradation in both the first and second weight loss events andare slightly shifted to lower temperatures for the PVC+ rubber PHAblend, the rate of degradation (the peak's height at the first stage ofdegradation) is lower in the presence of rubber PHA. The temperatures atthe maximum rate of degradation are also shifted to higher temperaturesfor both stages. Table 9 shows for each blend, the E_(a) for the firstand second weight loss events, the temperature at which 5% of theinitial sample weight is lost and the temperatures at maximumdegradation rate for both the first and second weight loss events at atemperature ramp rate of 20° C./min.

TABLE 9 Summary of TGA data for the PVC/PHA blends. Temp. at 5% E_(a,1)E_(a,2) T_(m1) Weight Loss Formulation (kJ/mole) (kJ/mole) (° C.) T_(m2)(° C.) (° C.) 2 116.3 252.7 304.5 457.0 287.7 6 115.7 287.2 308.0 463.0280.0 PVC + 28 phr 101.6 209.2 308.4 465.0 281.4 PHA E

The data in Table 9 shows that for the semi-rigid PVC with the additionof 10 phr PHA E, changes in the thermal degradation onset temperature,the temperatures at maximum degradation rates (T_(m1), T_(m2)) and thecorresponding activation energies (E_(a,1) and E_(a,2)) were notsignificant as compared to the PVC+18 phr DIDP sample. When theconcentration of PHA E was increased to 28 phr, however the activationenergies for thermal degradation were found to be lower by 13-17%.

Example 6 Addition of PHA to Flexible PVC—Effect on Thermal andMechanical Properties

In this example a flexible base PVC resin was first prepared containing36 phr DIDP plasticizer. To this flexible base resin was added PHA A (norubber PHA present), PHA B (no rubber PHA present), PHA C (40% rubberPHA) and PHA E (100% rubber PHA) as well as the acrylic polymerprocessing aid KANE ACE™ PA-20 in order to evaluate the effect theseadditives had on processing of the flexible PVC and the thermal andmechanical properties. Included in the mechanical tests was evaluationof the tear strength of the flexible PVC blends as this is an beneficialproperty for flexible plastic sheets and films due to the fact thatthese materials often fail in tearing mode.

Table 10 summarizes the thermal and mechanical test results obtained onthe flexible PVC formulations (#9-17) with various blend additives atloading levels of 5 phr and 15 phr. Also included in the table are theresults for the base flexible PVC resin with 36 phr DIDP plasticizeradded (formulation #9). The results showed that at the 5 phr loadinglevel, the additives composed of the PHA blends (PHA A, B and C) outperformed both the commercial acrylic polymer processing aid and PHA E(high molecular weight 100% P3HB-4HB rubber) in terms of lower T_(g)(higher plasticizing efficiency), higher tensile toughness and highertear strength. Additionally, it was qualitatively observed that theflexible PVC blends incorporating PHA B and C additives were opticallyclear and glossy. The data indicates that for flexible PVC's, additionof PHA having % crystallinity in the range of 25-40% impartsimprovements to the properties of the flexible PVC properties. Having upto 40% rubber PHA present in the PHA additive was shown to impart betterproperties to the flexible PVC in terms of toughness of and tearstrength. Higher levels of PHA rubber added to the flexible PVC did notimpart further improvements in toughness or tear strength.

At the 15 phr loading level for the PHA A, B and C additives, the DIDPplasticizer was able to be reduced without significant changes in theShore D hardness. The Tg for these blends was shown to increase whichindicates a higher softening point which could extend the applicationranges for these type of blends. The tear and tensile strength alsoshowed improvement as well. Addition of the PHA C additive appeared tohave the largest effect on the thermal and mechanical properties. ThisPHA was a ternary blend containing 40% by weight PHA rubber and is amultiphase crystalline material. However, FTIR data showed that theflexible PVC blends with PHA C at all loading levels were completelyamorphous. Even though PHA C and E are both rubbery materials, thebetter properties observed with the flexible PVC/PHA C blends versus theflexible PVC/PHA E blends could be due to the lower molecular weight ofthe PHA C material and also due to a better miscibility, morphologicalstructure and better melting properties of the PHA C material. Thereforeit appears that it is beneficial to optimize both the molecular weightand % 4HB in the PHA copolymer or copolymer blend for optimization ofthe properties of PVC/PHA blends.

FIG. 5 shows data for the elastic modulus (melt strength) of theflexible PVC with the additives PHA C (5 and 10 phr) and KANE ACE™ PA-20acrylic polymer (5 phr). These are plotted against the flexible PVC withno additives. These results showed that the addition of the acrylicpolymer significantly reduced the melt strength of the flexible PVC.Whereas when the PHA C was added at the 10 phr loading level, the meltstrength did not decrease.

TABLE 10 Summary of Flexible PVC@100 phr/PHA blends thermal andmechanical properties. PHA A, B and C are blends of PHB and P3HB-4HBcopolymers. PHA E is a single P3HB-4HB copolymer with 30% by weight 4HBcontent. The flexible PVC base resin was formulated with 25 or 36 phrDIDP plasticizer. Formu- Formu- Formu- Formu- Formu- Formu- Formu-Formu- Formu- lation 9 lation 10 lation 11 lation 12 lation 13 lation 14lation 15 lation 16 lation 17 DIDP 36 phr 36 phr 36 phr 25 phr 36 phr 25phr 36 phr 25 phr 36 phr KANE ™ ACE PA-20  5 phr PHA A  5 phr 15 phr PHAB  5 phr 15 phr PHA C  5 phr 15 phr PHA E  5 phr T_(g) (° C.) −5.3 −1.4−4.2 14.9 −5.9 14.1 −5.9 15.1 −1.84 Tensile Toughness (J) 4.10 1.17 4.124.14 4.14 4.10 3.82 4.21 1.72 Tensile Stress @ 100% 19 19 20 22 19 22 1922 15 elongation (MPa) Tear Strength (N/mm) — 31 51 60 50 58 51 64 30Shore D Hardness 37 44 35 41 36 42 37 42 37 Optical Clarity clear opaqueopaque opaque clear clear clear clear clear

Example 7 Addition of PHA Polymethylmethacrylate (PMMA)—Effect onThermal, Mechanical and Optical Properties

Blends of PMMA with PHA C and G at loading levels of 10, 20 and 30% byweight PHA were prepared and tested. PHA C and PHA G blends both containa high fraction of P3HB-4HB rubber copolymer (40% by weight of a 28-32%4HB copolymer). The solubility parameters of the comonomers of PHA C andG (3-hydroxybutyrate and 4-hydroxybutryate) and those for PMMA werecompared and are shown in Table 11.

TABLE 11 Van Krevelen solubility parameters and refractive indices(n_(D)) for monomers used in PMMA and PHA C and G. Total Polar Non-polarn_(D) (20° C.) Methyl methacrylate 20.4 27.3 17.1 1.4893 3-hydroxybutyrate 20.4 27.3 17.1 1.486-1.493 4-hydroxy butyrate 19.8 27.3 16.1 —

According to the calculated solubility parameters shown in Table 11,PMMA should be miscible with P3HB while the refractive indices of thesepolymers should also be close to each other. Previous work has shownthat isotactic, high molecular weight, crystalline P3HB was misciblewith PMMA up to 20% by weight loading of the P3HB (N. Lotti et. al.(1993), Polymer, 34, 4935; G. Ceccorulli et. al. (2002), J. Polym. Sci,Part B: Polym. Physics, vol. 401, 390). DMA data on the PMMA/PHA C and Gblends, summarized in Table 12, showed that at all PHA loading levels,only a single T_(g) was observed for the PMMA/PHA blends indicatingcomplete miscibility of these blends.

TABLE 12 Summary of DMA data for PMMA (PLEXIGLAS ™ 8N)/PHA blendsshowing T_(g) as a function of PHA loading. For comparison, the T_(g)for PMMA and PHA C are also shown. Material T_(g) (° C.) PMMA 113.14 PHAC −7.75 PMMA + 10% PHA C 114.58 PMMA + 20% PHA C 119.26 PMMA + 30% PHA C106.5 PMMA + 10% PHA G 109.11 PMMA + 20% PHA G 113.77 PMMA + 30% PHA G114.32

FTIR analysis of the PMMA/PHA blends also indicated that the P3HBpresent in the blends was in an amorphous (rubbery) state as evidencedby an increase in the absorbance peak at 1175-1180 cm-1 (correspondingto the amorphous P3HB band) as the loading of PHA C and G increased inthe blend. Visually it was observed that up to a loading level of 20%PHA by weight, the optical clarity of the PMMA was maintained. Howeverat PHA loadings greater than 20%, the optical clarity was attenuatedwith increasing PHA content in the blend. Measurement of optical lossesin the visible light region (600-750 nm) also showed that the PMMA/PHAblends transmitted about 56% more light in the 650-750 nm wavelengthregion than for pure PMMA alone.

Table 13 shows tensile and Notched Izod impact data for the 80% PMMA(PLEXIGLAS™ 8N)/20% PHA C blend. The results show that the tensiletoughness and impact strength of the PMMA increased by ˜75% afterblending with the PHA C. A corresponding increase in toughness andimpact strength of about 40% was seen with the 80% PMMA/20% PHA G ascompared to the pure PMMA. FIG. 6 shows a plot of tensile toughness vs.% PHA for PMMA/PHA C and G blends. It appears from the data that thetensile toughness maximized at about 20% PHA loading. Similar trendswere observed for the tensile elongation to break and the Notched Izodimpact strength.

TABLE 13 Summary of tensile and Notch Izod impact data for a blend of80% PMMA (PLEXIGLAS ™ 8N)/20% PHA C. For comparison, the same data for100% PMMA (PLEXIGLAS ™ 8N) is also included. Mechanical Property 100%PMMA 80% PMMA/20% PHA C Blend Tensile Modulus 1910 1560 (MPa) TensileElongation 4.7 7.0 @Break (%) Tensile Toughness (J) 0.26 0.45 NotchedIzod Impact 0.22 0.39 (ft lb/inch)

The effect on thermal stability of the adding PHA to PMMA (PLEXIGLAS™8N) was evaluated using torsional rheometry. FIG. 7 shows a plot of meltviscosity vs. shear rate at 160° C. for 100% PMMA and PMMA with 10% byweight PHA G. The plot shows that the melt viscosity curves for both the100% PMMA and PMMA/20% PHA G blend completely overlapped each other andtherefore there was no contribution to thermal degradation of the PMMAfrom the PHA G. Similar results were found for a plot of the meltstrength (G′) where no change contribution from the PHA to thermaldegradation of the PMMA was observed.

Example 8 Addition of PHA to Polyoxymethylene (POM)—Effect on NotchedIzod Impact Strength

In this example, PHA C and G (40% P3HB-4HB rubber copolymer with 28-32%4HB content) were blended at 5%, 10%, 20% and 30% by weight into POMresins KEPITAL™ F20-30 and KEPITAL™ F30-30 and tested for changes inimpact strength. For comparison, another POM resin, KEPITAL™ TE-21,having 5% TPU impact modifier was also tested for impact strength. FIG.8 shows an overlay plot of Notched Izod impact vs. PHA C concentrationfor the F20-03 and F30-03 POM resins. The data showed that the impactstrength of each POM resin increased to a maximum at 10-20% PHA Cconcentration. The Notched Izod impact improvement for the POM resinswas approximately 35%-50% for addition of PHA C. The impact strength ofthe TE-21 resin when compared to the F20-03 and F30-03 resins with 5%PHA C added was found to be lower. Tensile elongation was found tofollow the same trend as for the impact strength in these samples.Addition of PHA G to the POM resins did not show as large an effect onthe impact strength as found with PHA C.

Other than in the examples herein, or unless otherwise expresslyspecified, all of the numerical ranges, amounts, values and percentages,such as those for amounts of materials, elemental contents, times andtemperatures of reaction, ratios of amounts, and others, in thefollowing portion of the specification and attached claims may be readas if prefaced by the word “about” even though the term “about” may notexpressly appear with the value, amount, or range. Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties sought to be obtained by thepresent invention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains errornecessarily resulting from the standard deviation found in itsunderlying respective testing measurements. Furthermore, when numericalranges are set forth herein, these ranges are inclusive of the recitedrange end points (i.e., end points may be used). When percentages byweight are used herein, the numerical values reported are relative tothe total weight.

Also, it should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between (andincluding) the recited minimum value of 1 and the recited maximum valueof 10, that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10. The terms “one,” “a,” or “an”as used herein are intended to include “at least one” or “one or more,”unless otherwise indicated.

Any patent, publication, or other disclosure material, in whole or inpart, that is said to be incorporated by reference herein isincorporated herein only to the extent that the incorporated materialdoes not conflict with existing definitions, statements, or otherdisclosure material set forth in this disclosure. As such, and to theextent necessary, the disclosure as explicitly set forth hereinsupersedes any conflicting material incorporated herein by reference.Any material, or portion thereof, that is said to be incorporated byreference herein, but which conflicts with existing definitions,statements, or other disclosure material set forth herein will only beincorporated to the extent that no conflict arises between thatincorporated material and the existing disclosure material.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of the present invention, suitable methods andmaterials are described below. All publications, patent applications,patents, and other references mentioned herein are incorporated byreference in their entirety. In case of conflict, the presentspecification, including definitions, will control. In addition, thematerials, methods, and examples are illustrative only and not intendedto be limiting.

While this invention has been particularly shown and described withreferences to preferred embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the scope of the inventionencompassed by the appended claims.

What is claimed is:
 1. A composition, comprising: a polymer blend of: apolyvinyl chloride (PVC) polymer; and one or more biobasednon-extractable nonvolatile plasticizing polyhydroxyalkanoate (PHA)polymers, wherein the one or more PHA polymers improve performance ofthe polymer blend, and further wherein: the one or more PHA polymerscomprise: a blend of a) a poly(3-hydroxybutyrate) homopolymer and b) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate), wherein the content of4-hydroxybutyrate in (b) is 20-50% by weight of (b), and the content ofpolymer (a) in the blend is 5% to 95% by weight of the blend; a blend ofa) a poly(3-hydroxybutyrate) homopolymer and b) apoly(3-hydroxybutyrate-co-3-hydroxyvalerate), wherein the content of3-hydroxyvalerate is 20% to 50% by weight of b), and the content ofpolymer (a) in the blend is 5% to 95% by weight of the blend; a blend ofa) a poly(3-hydroxybutyrate) homopolymer blended with and b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate), wherein the content of3-hydroxyhexanoate in (b) is 5%-50% by weight of b), and the content ofpolymer (a) in the blend is 5% to 95% by weight of the blend; a blend ofa) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate), having the content of4-hydroxybutyrate of 5% to 15% by weight of a), and b)poly(3-hydroxybutyrate-co-4-hydroxybutyrate), having the content of4-hydroxybutyrate of 20-50% by weight of b), wherein the content ofpolymer (a) in the blend is 5% to 95% by weight of the blend; a blend ofa) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate), having the content of4-hydroxybutyrate of 5% to 15% by weight of a), and b)poly(3-hydroxybutyrate-co-5-hydroxyvalerate), having the content of5-hydroxyvalerate of 20% to 50% by weight of b), wherein the content ofpolymer (a) in the blend is 5% to 95% by weight of the blend; a blend ofa) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate), having the content of4-hydroxybutyrate of 5% to 15% by weight of a), and b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate), having the content of3-hydroxyhexanoate of 5%-50% by weight of b), and wherein the content ofpolymer (a) in the blend is 5% to 95% by weight of the blend; a blend ofa) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate), having the content of3-hydroxyvalerate of 5% to 22% by weight of a), and b)poly(3-hydroxybutyrate-co-4-hydroxybutyrate), having the content of4-hydroxybutyrate of 20-50% by weight of b), and wherein the content ofpolymer (a) in the blend is 5% to 95% by weight of the blend; a blend ofa) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate), having the content of3-hydroxyvalerate of 5% to 22% by weight of a), and b) apoly(3-hydroxybutyrate-co-5-hydroxyvalerate), having the content of5-hydroxyvalerate of 20% to 50% by weight of b), wherein the content ofpolymer (a) in the blend is 5% to 95% by weight of the blend; a blend ofa) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate), having the content of3-hydroxyvalerate of 5% to 22% by weight of a), and b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate), having the content of3-hydroxyhexanoate of 5%-50% by weight of b), and wherein the content ofpolymer (a) in the blend is 5% to 95% by weight of the blend; a blend ofa) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), having the contentof 3-hydroxyhexanoate of 3% to 15% by weight of a), and b) apoly(3-hydroxybutyrate-co-4-hydroxybutyrate), having the content of4-hydroxybutyrate of 20-50% by weight of b), and wherein the content ofthe polymer (a) in the blend is 5% to 95% by weight of the blend; ablend of a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), having thecontent of 3-hydroxyhexanoate of 3% to 15% by weight of a), and b) apoly(3-hydroxybutyrate-co-5-hydroxyvalerate), having the content of5-hydroxyvalerate of 20% to 50% by weight of b), and wherein the contentof polymer (a) in the blend is 5% to 95% by weight of the blend; or ablend of a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), having thecontent of 3-hydroxyhexanoate of 3% to 15% by weight of a), and b) apoly(3-hydroxybutyrate-co-3-hydroxyhexanoate), having the content of3-hydroxyhexanoate of 5%-50% by weight of b), and wherein the content ofpolymer (a) in the blend is 5% to 95% by weight of the blend, andfurther wherein the biobased content of the combined polymers (a) and(b) is 20% to 60% by weight of the combined polymers (a) and (b); andwherein the content of polymer (b) in the combined polymers (a) and (b)is 40% to 80% by weight of the combined weight of polymers (a) and (b).2. The composition of claim 1, further includingpoly(3-hydroxybutyrate-co-4-hydroxybutyrate), having the content of4-hydroxybutyrate of 20% to 50% by weight ofpoly(3-hydroxybutyrate-co-4-hydroxybutyrate).
 3. The composition ofclaim 1, further including poly(3-hydroxybutyrate-co-5-hydroxyvalerate),having the content of 5-hydroxyvalerate of 20% to 50% by weight ofpoly(3-hydroxybutyrate-co-5-hydroxyvalerate).
 4. The composition ofclaim 1, further includingpoly(3-hydroxybutyrate-co-3-hydroxyhexanoate), having the content of3-hydroxyhexanoate content of 5% to 50% by weight ofpoly(3-hydroxybutyrate-co-3-hydroxyhexanoate).
 5. The composition ofclaim 1, wherein the T_(g) of the polymer blend is from 10° C. to 35° C.